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The Vapor Pressure of
NISTIR 6643
Mercury
Marcia L HuberArno Laesecke
Daniel G Friend
NISTIR 6643
The Vapor Pressure of Mercury
Marcia L HuberArno Laesecke
Daniel G FriendPhysical and Chemical Properties Division
Chemical Science and Technology LaboratoryNational Institute of Standards and Technology
Boulder CO 80305-3328
April 2006
US DEPARTMENT OF COMMERCECarlos M Gutierrez Secretary
TECHNOLOGY ADMINISTRATIONRobert Cresanti Under Secretary of Commerce for Technology
NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGYWilliam Jeffrey Director
Table of Contents
1 Introduction1
2 Experimental Vapor Pressure Data 2
3 Correlation Development11
4 Comparison with Experimental Data18
5 Comparisons with Correlations from the Literature23
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC25
7 Conclusions35
8 References36
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of Mercury42
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury56
iii
The Vapor Pressure of Mercury
Marcia L Huber Arno Laesecke and Daniel G Friend
National Institute of Standards and TechnologylowastBoulder CO 80303-3328
In this report we review the available measurements of the vapor pressure of mercury and develop a new correlation that is valid from the triple point to the critical point The equation is a Wagner-type form where the terms of the equation are selected by use of a simulated annealing optimization algorithm In order to improve the reliability of the equation at low temperatures heat capacity data were used in addition to vapor pressure data We present comparisons with available experimental data and existing correlations In the region of interest for this project over the temperature range 0 degC to 60 degC the estimated uncertainty (estimated as a combined expanded uncertainty with coverage factor of 2 2σ) of the correlation is 1
Keywords correlation mercury vapor pressure
1 Introduction
Recent concerns about mercury as an industrial pollutant have lead to increased
interest in the detection and regulation of mercury in the environment [1] The
development of standardized equations for the thermophysical properties of mercury can
aid this task A critical evaluation of density thermal expansion coefficients and
compressibilities as a function of temperature and pressure was conducted by Holman
and ten Seldam [2] Bettin and Fehlauer [3] recently reviewed the density of mercury for
metrological applications Vukalovich and Fokinrsquos book [4] and the Gmelin Handbook
[5] are both thorough treatises on the thermophysical properties of mercury Thermal
properties such as thermal conductivity and heat capacity were reviewed by Sakonidou et
al [6] while Hensel and Warren [7] cover other properties including optical and
magnetic characteristics To assess risks of exposure it is important to have an accurate
lowast Physical and Chemical Properties Division Chemical Science and Technology Laboratory
1
representation of the vapor pressure of mercury Numerous compilations and correlations
of the vapor pressure of mercury have been published [8-25] but there is no consensus
on which is the best one to use for a given purpose In this work we review the existing
experimental data and correlations and provide a new representation of the vapor
pressure of mercury that is valid from the triple point to the critical point We also
present comparisons with both experimental data and correlations and estimate the
uncertainty of the correlation
2 Experimental Vapor Pressure Data
Experimental measurements of the vapor pressure of mercury have a long history
A single vapor pressure point of mercury the boiling point was first measured in 1801
by Dalton [26] who obtained a value corresponding to 622 K shortly thereafter in 1803
Crichton [27] mentioned that the normal boiling point is above a temperature
corresponding to 619 K More recently the normal boiling point of mercury was
determined by Beattie et al [28] as (35658 plusmn 00016) degC on the 1927 International
Temperature Scale This measurement was selected as a secondary fixed point on the
ITS-48 Temperature scale [29] Converted to the ITS-90 temperature scale [30] this
value is (6297653 plusmn 00016) K The value recommended by Marsh [31] is 62981 K
(IPTS-68) on the International Practical Temperature Scale [32] of 1968 this was a
secondary fixed point Converted to ITS-90 this recommendation is 6297683 K for the
normal boiling point
Regnault [33] published observations of the vapor pressure of mercury over a
range of temperatures in 1862 Several of the early publications are by researchers who
became quite famous including Avogadro [34] Dalton [26] Hertz [35] Ramsay [36]
and Haber [37] Indeed much of the work on mercury was done in the early part of the
20th century Figure 1 shows the distribution of the experimental data Table 1 gives a
detailed compilation of sources of vapor-pressure data from 1862 to the present along
with the temperature range of the measurements the experimental method used and an
estimate of the uncertainty of these measurements In general determinations of the
purity of the mercury were not available however methods for the purification of
mercury have been known for a long time and samples of high purity were prepared
2
before it was possible to quantify the purity [18] The estimates of uncertainty were
obtained by considering the experimental method and conditions the original authorrsquos
estimates (when available) and agreement with preliminary correlations These
correspond to our estimate of a combined expanded uncertainty with a coverage factor of
two In Appendix A we tabulate all experimental data for the vapor pressure of mercury
collected in this study
The experimental techniques used to measure vapor pressure can be grouped into
three main categories the static quasistatic and kinetic techniques are discussed by
Dykyj et al [38] and Ditchburn and Gilmour [14] One of the simplest methods to
measure the vapor pressure is a static method that involves placing the sample in a closed
container then removing any air and impurities keeping the vessel at constant
temperature and then measuring the temperature and pressure after equilibrium has been
established It is generally limited to pressures above 10 kPa In principle it is applicable
to any pressure but in practice the presence of nonvolatile impurities can cause large
systematic errors With very careful sample preparation it may be possible to go to lower
pressures with this technique Another static instrument is the isoteniscope This type of
instrument was used by Smith and Menzies [39 40] in their early work on the vapor
pressure of mercury In this type of apparatus the sample is placed in a bulb that is
connected to a U-tube that acts as a manometer (ie a pressure sensor) The device is
placed in a thermostat and the external pressure is adjusted until it equals that of the
vapor above the sample Isoteniscopes are limited by the sensitivity of the pressure
sensor A third type of static method involves the use of an inclined piston gauge The
sample is placed in a cylinder fitted with a movable piston so that the pressure of the
sample balances the weight (gravitational force) of the piston This method is generally
applicable over the range 01 kPa to 15 kPa
Among the instruments classified as quasistatic are ebulliometers and
transpiration methods In both of them a steady rate of boiling is established and it is
assumed that the pressure at steady state is equivalent to the equilibrium vapor pressure
In an ebulliometer the sample is boiled at a pressure set by an external pressurizing gas
(often helium) with the vapor passing through a reflux condenser before returning to the
boiler The temperature measured is that of the vapor just above the boiling liquid An
3
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
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[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
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36
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3] of ia PA 1968
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37
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[54] micron range
[55] ure of the
[56] mercury
[57]
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13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
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t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
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7
[75]
[76] 0degC (in German) Ann
1925
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[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
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(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
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temperature range 0-2000degC and pressure range of 200-5000 Atm Phys Metals Metallog 24(5) 74-89 1967
[104] Neale FE Cusack NE Thermoelectric power near the critical point of expanded fluid mercury J Phys F Metal Phys 9(1) 85-94 1979
[79] Rodebush WH Dixon AL The vapor pressures of metals a new experimental method PhyRev 26 851-858 1
[80] Roeder A Morawietz W Investigations on the occurrence of compound molecules in the vapof potassium-merc
[81] Ruff O Bergdahl B Studies at high temperatures XII The measurement of vapor tensions at very high temperatures and some observations of the solubility of carbon in metalsAnorg Allg Chem 106 76-94 1919 Schmahl NG Barthel J Kaloff H An apparatus for vapor pressure measurements at elevated temperatures with a static mZ Phys Chem 46(3-4) 183-189 1965 Schneider A Schupp K The Phys Chem 50 163-167 1944 Schoumlnherr Gnear the critical point of the almost pure solvent Ber Bunsenges Phys Chem 85 361-367 1981Scott DH A determination of the vapotheir chemical constants Phil Mag 47 32-50 1924 Shpilrain EE Nikanorov EV Measurement of the vapor pressurepoint method High Temp 9 585-587 1971
[87] Spedding FH Dye JL The vapor pressure of mercury at 250-360deg J Phys Chem 59 581-1955
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Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
NISTIR 6643
The Vapor Pressure of Mercury
Marcia L HuberArno Laesecke
Daniel G FriendPhysical and Chemical Properties Division
Chemical Science and Technology LaboratoryNational Institute of Standards and Technology
Boulder CO 80305-3328
April 2006
US DEPARTMENT OF COMMERCECarlos M Gutierrez Secretary
TECHNOLOGY ADMINISTRATIONRobert Cresanti Under Secretary of Commerce for Technology
NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGYWilliam Jeffrey Director
Table of Contents
1 Introduction1
2 Experimental Vapor Pressure Data 2
3 Correlation Development11
4 Comparison with Experimental Data18
5 Comparisons with Correlations from the Literature23
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC25
7 Conclusions35
8 References36
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of Mercury42
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury56
iii
The Vapor Pressure of Mercury
Marcia L Huber Arno Laesecke and Daniel G Friend
National Institute of Standards and TechnologylowastBoulder CO 80303-3328
In this report we review the available measurements of the vapor pressure of mercury and develop a new correlation that is valid from the triple point to the critical point The equation is a Wagner-type form where the terms of the equation are selected by use of a simulated annealing optimization algorithm In order to improve the reliability of the equation at low temperatures heat capacity data were used in addition to vapor pressure data We present comparisons with available experimental data and existing correlations In the region of interest for this project over the temperature range 0 degC to 60 degC the estimated uncertainty (estimated as a combined expanded uncertainty with coverage factor of 2 2σ) of the correlation is 1
Keywords correlation mercury vapor pressure
1 Introduction
Recent concerns about mercury as an industrial pollutant have lead to increased
interest in the detection and regulation of mercury in the environment [1] The
development of standardized equations for the thermophysical properties of mercury can
aid this task A critical evaluation of density thermal expansion coefficients and
compressibilities as a function of temperature and pressure was conducted by Holman
and ten Seldam [2] Bettin and Fehlauer [3] recently reviewed the density of mercury for
metrological applications Vukalovich and Fokinrsquos book [4] and the Gmelin Handbook
[5] are both thorough treatises on the thermophysical properties of mercury Thermal
properties such as thermal conductivity and heat capacity were reviewed by Sakonidou et
al [6] while Hensel and Warren [7] cover other properties including optical and
magnetic characteristics To assess risks of exposure it is important to have an accurate
lowast Physical and Chemical Properties Division Chemical Science and Technology Laboratory
1
representation of the vapor pressure of mercury Numerous compilations and correlations
of the vapor pressure of mercury have been published [8-25] but there is no consensus
on which is the best one to use for a given purpose In this work we review the existing
experimental data and correlations and provide a new representation of the vapor
pressure of mercury that is valid from the triple point to the critical point We also
present comparisons with both experimental data and correlations and estimate the
uncertainty of the correlation
2 Experimental Vapor Pressure Data
Experimental measurements of the vapor pressure of mercury have a long history
A single vapor pressure point of mercury the boiling point was first measured in 1801
by Dalton [26] who obtained a value corresponding to 622 K shortly thereafter in 1803
Crichton [27] mentioned that the normal boiling point is above a temperature
corresponding to 619 K More recently the normal boiling point of mercury was
determined by Beattie et al [28] as (35658 plusmn 00016) degC on the 1927 International
Temperature Scale This measurement was selected as a secondary fixed point on the
ITS-48 Temperature scale [29] Converted to the ITS-90 temperature scale [30] this
value is (6297653 plusmn 00016) K The value recommended by Marsh [31] is 62981 K
(IPTS-68) on the International Practical Temperature Scale [32] of 1968 this was a
secondary fixed point Converted to ITS-90 this recommendation is 6297683 K for the
normal boiling point
Regnault [33] published observations of the vapor pressure of mercury over a
range of temperatures in 1862 Several of the early publications are by researchers who
became quite famous including Avogadro [34] Dalton [26] Hertz [35] Ramsay [36]
and Haber [37] Indeed much of the work on mercury was done in the early part of the
20th century Figure 1 shows the distribution of the experimental data Table 1 gives a
detailed compilation of sources of vapor-pressure data from 1862 to the present along
with the temperature range of the measurements the experimental method used and an
estimate of the uncertainty of these measurements In general determinations of the
purity of the mercury were not available however methods for the purification of
mercury have been known for a long time and samples of high purity were prepared
2
before it was possible to quantify the purity [18] The estimates of uncertainty were
obtained by considering the experimental method and conditions the original authorrsquos
estimates (when available) and agreement with preliminary correlations These
correspond to our estimate of a combined expanded uncertainty with a coverage factor of
two In Appendix A we tabulate all experimental data for the vapor pressure of mercury
collected in this study
The experimental techniques used to measure vapor pressure can be grouped into
three main categories the static quasistatic and kinetic techniques are discussed by
Dykyj et al [38] and Ditchburn and Gilmour [14] One of the simplest methods to
measure the vapor pressure is a static method that involves placing the sample in a closed
container then removing any air and impurities keeping the vessel at constant
temperature and then measuring the temperature and pressure after equilibrium has been
established It is generally limited to pressures above 10 kPa In principle it is applicable
to any pressure but in practice the presence of nonvolatile impurities can cause large
systematic errors With very careful sample preparation it may be possible to go to lower
pressures with this technique Another static instrument is the isoteniscope This type of
instrument was used by Smith and Menzies [39 40] in their early work on the vapor
pressure of mercury In this type of apparatus the sample is placed in a bulb that is
connected to a U-tube that acts as a manometer (ie a pressure sensor) The device is
placed in a thermostat and the external pressure is adjusted until it equals that of the
vapor above the sample Isoteniscopes are limited by the sensitivity of the pressure
sensor A third type of static method involves the use of an inclined piston gauge The
sample is placed in a cylinder fitted with a movable piston so that the pressure of the
sample balances the weight (gravitational force) of the piston This method is generally
applicable over the range 01 kPa to 15 kPa
Among the instruments classified as quasistatic are ebulliometers and
transpiration methods In both of them a steady rate of boiling is established and it is
assumed that the pressure at steady state is equivalent to the equilibrium vapor pressure
In an ebulliometer the sample is boiled at a pressure set by an external pressurizing gas
(often helium) with the vapor passing through a reflux condenser before returning to the
boiler The temperature measured is that of the vapor just above the boiling liquid An
3
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
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[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Table of Contents
1 Introduction1
2 Experimental Vapor Pressure Data 2
3 Correlation Development11
4 Comparison with Experimental Data18
5 Comparisons with Correlations from the Literature23
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC25
7 Conclusions35
8 References36
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of Mercury42
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury56
iii
The Vapor Pressure of Mercury
Marcia L Huber Arno Laesecke and Daniel G Friend
National Institute of Standards and TechnologylowastBoulder CO 80303-3328
In this report we review the available measurements of the vapor pressure of mercury and develop a new correlation that is valid from the triple point to the critical point The equation is a Wagner-type form where the terms of the equation are selected by use of a simulated annealing optimization algorithm In order to improve the reliability of the equation at low temperatures heat capacity data were used in addition to vapor pressure data We present comparisons with available experimental data and existing correlations In the region of interest for this project over the temperature range 0 degC to 60 degC the estimated uncertainty (estimated as a combined expanded uncertainty with coverage factor of 2 2σ) of the correlation is 1
Keywords correlation mercury vapor pressure
1 Introduction
Recent concerns about mercury as an industrial pollutant have lead to increased
interest in the detection and regulation of mercury in the environment [1] The
development of standardized equations for the thermophysical properties of mercury can
aid this task A critical evaluation of density thermal expansion coefficients and
compressibilities as a function of temperature and pressure was conducted by Holman
and ten Seldam [2] Bettin and Fehlauer [3] recently reviewed the density of mercury for
metrological applications Vukalovich and Fokinrsquos book [4] and the Gmelin Handbook
[5] are both thorough treatises on the thermophysical properties of mercury Thermal
properties such as thermal conductivity and heat capacity were reviewed by Sakonidou et
al [6] while Hensel and Warren [7] cover other properties including optical and
magnetic characteristics To assess risks of exposure it is important to have an accurate
lowast Physical and Chemical Properties Division Chemical Science and Technology Laboratory
1
representation of the vapor pressure of mercury Numerous compilations and correlations
of the vapor pressure of mercury have been published [8-25] but there is no consensus
on which is the best one to use for a given purpose In this work we review the existing
experimental data and correlations and provide a new representation of the vapor
pressure of mercury that is valid from the triple point to the critical point We also
present comparisons with both experimental data and correlations and estimate the
uncertainty of the correlation
2 Experimental Vapor Pressure Data
Experimental measurements of the vapor pressure of mercury have a long history
A single vapor pressure point of mercury the boiling point was first measured in 1801
by Dalton [26] who obtained a value corresponding to 622 K shortly thereafter in 1803
Crichton [27] mentioned that the normal boiling point is above a temperature
corresponding to 619 K More recently the normal boiling point of mercury was
determined by Beattie et al [28] as (35658 plusmn 00016) degC on the 1927 International
Temperature Scale This measurement was selected as a secondary fixed point on the
ITS-48 Temperature scale [29] Converted to the ITS-90 temperature scale [30] this
value is (6297653 plusmn 00016) K The value recommended by Marsh [31] is 62981 K
(IPTS-68) on the International Practical Temperature Scale [32] of 1968 this was a
secondary fixed point Converted to ITS-90 this recommendation is 6297683 K for the
normal boiling point
Regnault [33] published observations of the vapor pressure of mercury over a
range of temperatures in 1862 Several of the early publications are by researchers who
became quite famous including Avogadro [34] Dalton [26] Hertz [35] Ramsay [36]
and Haber [37] Indeed much of the work on mercury was done in the early part of the
20th century Figure 1 shows the distribution of the experimental data Table 1 gives a
detailed compilation of sources of vapor-pressure data from 1862 to the present along
with the temperature range of the measurements the experimental method used and an
estimate of the uncertainty of these measurements In general determinations of the
purity of the mercury were not available however methods for the purification of
mercury have been known for a long time and samples of high purity were prepared
2
before it was possible to quantify the purity [18] The estimates of uncertainty were
obtained by considering the experimental method and conditions the original authorrsquos
estimates (when available) and agreement with preliminary correlations These
correspond to our estimate of a combined expanded uncertainty with a coverage factor of
two In Appendix A we tabulate all experimental data for the vapor pressure of mercury
collected in this study
The experimental techniques used to measure vapor pressure can be grouped into
three main categories the static quasistatic and kinetic techniques are discussed by
Dykyj et al [38] and Ditchburn and Gilmour [14] One of the simplest methods to
measure the vapor pressure is a static method that involves placing the sample in a closed
container then removing any air and impurities keeping the vessel at constant
temperature and then measuring the temperature and pressure after equilibrium has been
established It is generally limited to pressures above 10 kPa In principle it is applicable
to any pressure but in practice the presence of nonvolatile impurities can cause large
systematic errors With very careful sample preparation it may be possible to go to lower
pressures with this technique Another static instrument is the isoteniscope This type of
instrument was used by Smith and Menzies [39 40] in their early work on the vapor
pressure of mercury In this type of apparatus the sample is placed in a bulb that is
connected to a U-tube that acts as a manometer (ie a pressure sensor) The device is
placed in a thermostat and the external pressure is adjusted until it equals that of the
vapor above the sample Isoteniscopes are limited by the sensitivity of the pressure
sensor A third type of static method involves the use of an inclined piston gauge The
sample is placed in a cylinder fitted with a movable piston so that the pressure of the
sample balances the weight (gravitational force) of the piston This method is generally
applicable over the range 01 kPa to 15 kPa
Among the instruments classified as quasistatic are ebulliometers and
transpiration methods In both of them a steady rate of boiling is established and it is
assumed that the pressure at steady state is equivalent to the equilibrium vapor pressure
In an ebulliometer the sample is boiled at a pressure set by an external pressurizing gas
(often helium) with the vapor passing through a reflux condenser before returning to the
boiler The temperature measured is that of the vapor just above the boiling liquid An
3
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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e thermodynamic
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Te Volum2] Lide ed CRC o Chemistry
Rato3] KDB
2004 ea Thermo al erties Data (KDB) h w orgkdb Korea
ersity[13 ley J ng W Osc Row DIADE DIPP tion a
Eval nager 70 oun ity Prov UT 2[135] Yaws CL l Prop rties H Phys modyna ics En l
sport Health elate s for amp Inorg ic Che Grawssion 784 p
[13 aftik les on e The l Pro Liquids nd Ga ork ted Pr 2nd e
[13 ley R al com unic ber M ham Yo g Uni vo Ut2 20
[13 e E w DN Evalu ermo unctions rom eq onstans Far 2 539- 47 1
[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
24 [142] olmer M Estermann I On the evaporation coeff of solid a d liquid m (in
erman) Zeitschr f Physik 7 1-12 1921 [143] witt FB method of determ e llic vapou an
perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
The Vapor Pressure of Mercury
Marcia L Huber Arno Laesecke and Daniel G Friend
National Institute of Standards and TechnologylowastBoulder CO 80303-3328
In this report we review the available measurements of the vapor pressure of mercury and develop a new correlation that is valid from the triple point to the critical point The equation is a Wagner-type form where the terms of the equation are selected by use of a simulated annealing optimization algorithm In order to improve the reliability of the equation at low temperatures heat capacity data were used in addition to vapor pressure data We present comparisons with available experimental data and existing correlations In the region of interest for this project over the temperature range 0 degC to 60 degC the estimated uncertainty (estimated as a combined expanded uncertainty with coverage factor of 2 2σ) of the correlation is 1
Keywords correlation mercury vapor pressure
1 Introduction
Recent concerns about mercury as an industrial pollutant have lead to increased
interest in the detection and regulation of mercury in the environment [1] The
development of standardized equations for the thermophysical properties of mercury can
aid this task A critical evaluation of density thermal expansion coefficients and
compressibilities as a function of temperature and pressure was conducted by Holman
and ten Seldam [2] Bettin and Fehlauer [3] recently reviewed the density of mercury for
metrological applications Vukalovich and Fokinrsquos book [4] and the Gmelin Handbook
[5] are both thorough treatises on the thermophysical properties of mercury Thermal
properties such as thermal conductivity and heat capacity were reviewed by Sakonidou et
al [6] while Hensel and Warren [7] cover other properties including optical and
magnetic characteristics To assess risks of exposure it is important to have an accurate
lowast Physical and Chemical Properties Division Chemical Science and Technology Laboratory
1
representation of the vapor pressure of mercury Numerous compilations and correlations
of the vapor pressure of mercury have been published [8-25] but there is no consensus
on which is the best one to use for a given purpose In this work we review the existing
experimental data and correlations and provide a new representation of the vapor
pressure of mercury that is valid from the triple point to the critical point We also
present comparisons with both experimental data and correlations and estimate the
uncertainty of the correlation
2 Experimental Vapor Pressure Data
Experimental measurements of the vapor pressure of mercury have a long history
A single vapor pressure point of mercury the boiling point was first measured in 1801
by Dalton [26] who obtained a value corresponding to 622 K shortly thereafter in 1803
Crichton [27] mentioned that the normal boiling point is above a temperature
corresponding to 619 K More recently the normal boiling point of mercury was
determined by Beattie et al [28] as (35658 plusmn 00016) degC on the 1927 International
Temperature Scale This measurement was selected as a secondary fixed point on the
ITS-48 Temperature scale [29] Converted to the ITS-90 temperature scale [30] this
value is (6297653 plusmn 00016) K The value recommended by Marsh [31] is 62981 K
(IPTS-68) on the International Practical Temperature Scale [32] of 1968 this was a
secondary fixed point Converted to ITS-90 this recommendation is 6297683 K for the
normal boiling point
Regnault [33] published observations of the vapor pressure of mercury over a
range of temperatures in 1862 Several of the early publications are by researchers who
became quite famous including Avogadro [34] Dalton [26] Hertz [35] Ramsay [36]
and Haber [37] Indeed much of the work on mercury was done in the early part of the
20th century Figure 1 shows the distribution of the experimental data Table 1 gives a
detailed compilation of sources of vapor-pressure data from 1862 to the present along
with the temperature range of the measurements the experimental method used and an
estimate of the uncertainty of these measurements In general determinations of the
purity of the mercury were not available however methods for the purification of
mercury have been known for a long time and samples of high purity were prepared
2
before it was possible to quantify the purity [18] The estimates of uncertainty were
obtained by considering the experimental method and conditions the original authorrsquos
estimates (when available) and agreement with preliminary correlations These
correspond to our estimate of a combined expanded uncertainty with a coverage factor of
two In Appendix A we tabulate all experimental data for the vapor pressure of mercury
collected in this study
The experimental techniques used to measure vapor pressure can be grouped into
three main categories the static quasistatic and kinetic techniques are discussed by
Dykyj et al [38] and Ditchburn and Gilmour [14] One of the simplest methods to
measure the vapor pressure is a static method that involves placing the sample in a closed
container then removing any air and impurities keeping the vessel at constant
temperature and then measuring the temperature and pressure after equilibrium has been
established It is generally limited to pressures above 10 kPa In principle it is applicable
to any pressure but in practice the presence of nonvolatile impurities can cause large
systematic errors With very careful sample preparation it may be possible to go to lower
pressures with this technique Another static instrument is the isoteniscope This type of
instrument was used by Smith and Menzies [39 40] in their early work on the vapor
pressure of mercury In this type of apparatus the sample is placed in a bulb that is
connected to a U-tube that acts as a manometer (ie a pressure sensor) The device is
placed in a thermostat and the external pressure is adjusted until it equals that of the
vapor above the sample Isoteniscopes are limited by the sensitivity of the pressure
sensor A third type of static method involves the use of an inclined piston gauge The
sample is placed in a cylinder fitted with a movable piston so that the pressure of the
sample balances the weight (gravitational force) of the piston This method is generally
applicable over the range 01 kPa to 15 kPa
Among the instruments classified as quasistatic are ebulliometers and
transpiration methods In both of them a steady rate of boiling is established and it is
assumed that the pressure at steady state is equivalent to the equilibrium vapor pressure
In an ebulliometer the sample is boiled at a pressure set by an external pressurizing gas
(often helium) with the vapor passing through a reflux condenser before returning to the
boiler The temperature measured is that of the vapor just above the boiling liquid An
3
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
[26] Dalton J Experimental Essays II On the force of steam or vapour from water and various other liquids both in a vacuum and in air Mem Proc - Manchester Lit Philos Soc 5(2) 550-574
[27] g point of tin and the boiling point of mercury with a description of a
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[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
Oxford UK 1987
[34] mpfs bei verschiedenen Temperaturen
[35] (in German) Ann Phys Chem 17 193-200 1882
an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
[45] Colardeau E Riviegravere C Recherches sur les tensions de le vapeur de mercure
at
[47] he determination of high precision vapour pressure of mercury and its
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lumbia Vancouver Canada 1950
1801 Crichton J On the freezinself-registering thermometer Phil Mag (March) 147-148 1803 Beattie JA Blaisdell BE Kaminsky J An experimental study of the absolute tescale IV Reproducibility of the mercury boiling point The effect of pressure on the mercury boiling point Proc Am Acad Arts Sci 71 375-385 1937 Hall JA Barber CR The Internation1(4) 81-85 1950 Preston-Thomas H The international temperature scale of 1990 (ITS-90) Metrologia 27 3-10 1990
[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
[32] Preston-Thomas H The international practical temperature scale of 1968 amended edition of 1975 Metrologia 12 7-17 1976
[33] Regnault V Forces eacutelastiques des vapeurs Mem Acad Sci Inst Fr 26 506-525 1862 Avogadro A Ueber die Spannkraft des QuecksilberdaPogg Ann 27 60-80 1833 Hertz H On the pressure of saturated mercury
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[39] Smith A Menzies AWC Studies in vapor pressure IV A redetermination of the vapor pressures of mercury from 250deg to 435deg J Am C
[40] Menzies AWC The vapour pressures of liquid mercury Z Phys Chem 130 90-94 192[41] Bernhardt F Saturation pressure of mercury up to 2000 kgcm2 (in German) Phys Z 26(6) 265-
275 1925 [4 Bessel-Hagen E Ueber eine neue Form der Toumlplerschen Quecksilberluftpumpe und einige mit i
angestellte Versuche Ann Phys Chem 12(2) 425-445 1881 [4 Burlingame JW Dilute solutions of mercury in liquid binary alloys PhD Thesis University
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properties of solid liquid and ga809 1953 Cailletet L satureacutee Compt Rend 130 1585-1591 1900
[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
[49] Dauphinee TM The measurement of the vapour pressure of mercury in the intermediate pressure range PhD Thesis University of British Co
37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
[53] cadmium and mercury Phil Mag 33(193) 33-48
[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
[59] ohen Drucken Ber Bunsenges Phys Chem 70(910) 1154-1160 1966
13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
[65] 4
t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
[52] Durrans TH A treatise on distillation Perfumery and Essential Oil Record 11S 154-198 1920Egerton AC The vapour pressure of zinc1917 Ernsberger FM Pitman HW New absolute manometer for vapor pressures in theRev Sci Instrum 26(6) 584-589 1955 Galchenko IE Pelevin OV Sokolov AM Determination of the partial vapor pressvolatile component by the static method Industrial Laboratory 44(12) 1699-1700 1978 Galchenko IE Pelevin OV Sokolov AM Determination of the vapor pressure ofover melts in the Hg-Cd-Te system Inorganic Materials 20(7) 952-955 1984 Gebhardt A Uumlber den Dampfdruck von Quecksilber und Natrium Ber Dtsch Phys Ges 7 184-185 1905 HagenPhys Chem 16 610-618 1882 Hensel F Franck EU Elektrische Leitfaumlhigkeit und Dichte von uumlberkritischem gasfoumlrmigem Quecksilber unter h
[60] Heycock CT Lamplough FEE The boiling points of mercury cadmium zinc potassium and sodium Proc Chem Soc 28 3-4 19
[61] Hildenbrand DL Hall WF Ju F Potter ND Vapor pressures and vapor thermodynamic properties of some lithium and magnesium halides J C
[62] Hill CF Measurement of mercury vapor pressure by means of the Knudsen pressure gauge PhyRev 20 259-266 1922
[63] Hubbard SR Ross RG Slope anomaly in the vapour pressure curve of Hg Nature 295 6683 1982 Jenkins CHM The determodified manometric method Proc R Soc London A 110(754) 456-463 1926 Kahlbaum GWA Studies of vapor pressure measurements (in German) Z Phys Chem 13 14-55 189
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
representation of the vapor pressure of mercury Numerous compilations and correlations
of the vapor pressure of mercury have been published [8-25] but there is no consensus
on which is the best one to use for a given purpose In this work we review the existing
experimental data and correlations and provide a new representation of the vapor
pressure of mercury that is valid from the triple point to the critical point We also
present comparisons with both experimental data and correlations and estimate the
uncertainty of the correlation
2 Experimental Vapor Pressure Data
Experimental measurements of the vapor pressure of mercury have a long history
A single vapor pressure point of mercury the boiling point was first measured in 1801
by Dalton [26] who obtained a value corresponding to 622 K shortly thereafter in 1803
Crichton [27] mentioned that the normal boiling point is above a temperature
corresponding to 619 K More recently the normal boiling point of mercury was
determined by Beattie et al [28] as (35658 plusmn 00016) degC on the 1927 International
Temperature Scale This measurement was selected as a secondary fixed point on the
ITS-48 Temperature scale [29] Converted to the ITS-90 temperature scale [30] this
value is (6297653 plusmn 00016) K The value recommended by Marsh [31] is 62981 K
(IPTS-68) on the International Practical Temperature Scale [32] of 1968 this was a
secondary fixed point Converted to ITS-90 this recommendation is 6297683 K for the
normal boiling point
Regnault [33] published observations of the vapor pressure of mercury over a
range of temperatures in 1862 Several of the early publications are by researchers who
became quite famous including Avogadro [34] Dalton [26] Hertz [35] Ramsay [36]
and Haber [37] Indeed much of the work on mercury was done in the early part of the
20th century Figure 1 shows the distribution of the experimental data Table 1 gives a
detailed compilation of sources of vapor-pressure data from 1862 to the present along
with the temperature range of the measurements the experimental method used and an
estimate of the uncertainty of these measurements In general determinations of the
purity of the mercury were not available however methods for the purification of
mercury have been known for a long time and samples of high purity were prepared
2
before it was possible to quantify the purity [18] The estimates of uncertainty were
obtained by considering the experimental method and conditions the original authorrsquos
estimates (when available) and agreement with preliminary correlations These
correspond to our estimate of a combined expanded uncertainty with a coverage factor of
two In Appendix A we tabulate all experimental data for the vapor pressure of mercury
collected in this study
The experimental techniques used to measure vapor pressure can be grouped into
three main categories the static quasistatic and kinetic techniques are discussed by
Dykyj et al [38] and Ditchburn and Gilmour [14] One of the simplest methods to
measure the vapor pressure is a static method that involves placing the sample in a closed
container then removing any air and impurities keeping the vessel at constant
temperature and then measuring the temperature and pressure after equilibrium has been
established It is generally limited to pressures above 10 kPa In principle it is applicable
to any pressure but in practice the presence of nonvolatile impurities can cause large
systematic errors With very careful sample preparation it may be possible to go to lower
pressures with this technique Another static instrument is the isoteniscope This type of
instrument was used by Smith and Menzies [39 40] in their early work on the vapor
pressure of mercury In this type of apparatus the sample is placed in a bulb that is
connected to a U-tube that acts as a manometer (ie a pressure sensor) The device is
placed in a thermostat and the external pressure is adjusted until it equals that of the
vapor above the sample Isoteniscopes are limited by the sensitivity of the pressure
sensor A third type of static method involves the use of an inclined piston gauge The
sample is placed in a cylinder fitted with a movable piston so that the pressure of the
sample balances the weight (gravitational force) of the piston This method is generally
applicable over the range 01 kPa to 15 kPa
Among the instruments classified as quasistatic are ebulliometers and
transpiration methods In both of them a steady rate of boiling is established and it is
assumed that the pressure at steady state is equivalent to the equilibrium vapor pressure
In an ebulliometer the sample is boiled at a pressure set by an external pressurizing gas
(often helium) with the vapor passing through a reflux condenser before returning to the
boiler The temperature measured is that of the vapor just above the boiling liquid An
3
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
before it was possible to quantify the purity [18] The estimates of uncertainty were
obtained by considering the experimental method and conditions the original authorrsquos
estimates (when available) and agreement with preliminary correlations These
correspond to our estimate of a combined expanded uncertainty with a coverage factor of
two In Appendix A we tabulate all experimental data for the vapor pressure of mercury
collected in this study
The experimental techniques used to measure vapor pressure can be grouped into
three main categories the static quasistatic and kinetic techniques are discussed by
Dykyj et al [38] and Ditchburn and Gilmour [14] One of the simplest methods to
measure the vapor pressure is a static method that involves placing the sample in a closed
container then removing any air and impurities keeping the vessel at constant
temperature and then measuring the temperature and pressure after equilibrium has been
established It is generally limited to pressures above 10 kPa In principle it is applicable
to any pressure but in practice the presence of nonvolatile impurities can cause large
systematic errors With very careful sample preparation it may be possible to go to lower
pressures with this technique Another static instrument is the isoteniscope This type of
instrument was used by Smith and Menzies [39 40] in their early work on the vapor
pressure of mercury In this type of apparatus the sample is placed in a bulb that is
connected to a U-tube that acts as a manometer (ie a pressure sensor) The device is
placed in a thermostat and the external pressure is adjusted until it equals that of the
vapor above the sample Isoteniscopes are limited by the sensitivity of the pressure
sensor A third type of static method involves the use of an inclined piston gauge The
sample is placed in a cylinder fitted with a movable piston so that the pressure of the
sample balances the weight (gravitational force) of the piston This method is generally
applicable over the range 01 kPa to 15 kPa
Among the instruments classified as quasistatic are ebulliometers and
transpiration methods In both of them a steady rate of boiling is established and it is
assumed that the pressure at steady state is equivalent to the equilibrium vapor pressure
In an ebulliometer the sample is boiled at a pressure set by an external pressurizing gas
(often helium) with the vapor passing through a reflux condenser before returning to the
boiler The temperature measured is that of the vapor just above the boiling liquid An
3
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
advantage to this method is that volatile impurities do not condense and are removed at
the top of the apparatus This method may also be set up in a comparative mode with two
separate ebulliometers one containing a reference fluid and the other containing the
sample fluid connected with a common pressure line so that direct measurement of the
pressure is unnecessary It is possible to make very accurate measurements with this type
of device at pressures greater than about 2 kPa The very accurate measurements of the
vapor pressure of mercury by Ambrose and Sprake [18] were made with an ebulliometric
technique The transpiration method (also called gas saturation) involves passing a steady
stream of an inert gas over or through the sample which is held at constant temperature
The pressure is not measured directly but rather is calculated from converting the
concentration of the mercury in the gas stream to a partial pressure that is the vapor
pressure of the sample This type of method has a larger uncertainty than some of the
other methods generally ranging from 05 to 5 [38] It is most useful over a pressure
range of 01 to 5 kPa For example Burlingame [43] and Dauphinee [4950] used the
transpiration method in their measurements
4
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
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[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
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[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
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me or estab ti our pressu quations ic 1974 11] Wa W Ew en W New ur-pressu nd a new nal
vap12] Wa
ressure W Ein
foat
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Gle gen - g B er Dampf kkurve re e Duumlsseldor G VD lag Gm ch chte der V Zeitschrif S No 39 18 197
13] Lem EW Goodwin ARH Critical propeCnH normal alkanes with nlt=36 and isom or n=4 th 9 Chem R ata 29( 39 200
14] Pol E Pra nell JP T ropertie s a ds New Y NY Mc -Hill 5 p
15] Ew B Sa h apor pres of acet et by compa e ebu
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g 9 486-491lation for
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poi the criti J hem Ref 31(1) 217] Wa W Pru ern
sub e Revis di Internatio Tempera e J Phys C Ref Dat 783-78
18] Wa W Pru e I ormulatio 95 for thord water su fo l and scien use J P m ta 31(2) -535 200
19] Kin B Al-N A for corre and ext ap sure data t wer tembel
al po
pour pressm Eng S
n74
at temper es e norma 9(4) 100
20] Till oth R ea ion analys r estimat em e vapor pr res and alpies of ti ed to refri ts Int J ph ) 1365-13 1996
21] Mo J Taylo O recommended values of am hysical co ts 200 ev Mod (1 2005
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24] Kir671
ick S G 1983
d g Scienc 0
25] Pre H Flan P er ipes The f Sci ic Compu b K Camb e Univer s 986
26] Lun M Mees ve f an anne algorith P 111-124 27] Hu ML Stru ti a
thre ld acceptin ca 134a Co28] Bog PT Byrd Ro Schnab B ODR o rt
Dis e Regress TI Natl Inst nd Techn 29] Los
0] Lange NA ed Handbook of ChemD Atomi ts ements P
istry 10th ed McGraw-Hill New York 1967 ppl Che
[1
40
[131] Washburn EW ed International Critical Tables of Numerical Data Physics Chemistry and chnology e III McGraw-Hill New York 1928
[13 DR Handb ok of and Physics 85th Edition ed CRC Press Boca n FL
[13 Kor physic Prop bank ttpww cheric
Te Volum2] Lide ed CRC o Chemistry
Rato3] KDB
2004 ea Thermo al erties Data (KDB) h w orgkdb Korea
ersity[13 ley J ng W Osc Row DIADE DIPP tion a
Eval nager 70 oun ity Prov UT 2[135] Yaws CL l Prop rties H Phys modyna ics En l
sport Health elate s for amp Inorg ic Che Grawssion 784 p
[13 aftik les on e The l Pro Liquids nd Ga ork ted Pr 2nd e
[13 ley R al com unic ber M ham Yo g Uni vo Ut2 20
[13 e E w DN Evalu ermo unctions rom eq onstans Far 2 539- 47 1
[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
24 [142] olmer M Estermann I On the evaporation coeff of solid a d liquid m (in
erman) Zeitschr f Physik 7 1-12 1921 [143] witt FB method of determ e llic vapou an
perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
1E-9
1E-6
1E-3
1E+0
1E+3
1E+6
100
300
500
700
900
1100
1300
1500
1700
Tem
pera
ture
K
Pressure kPaR
egna
ult 1
862
Her
tz 1
882
Ram
say
1886
Cal
lend
ar 1
891
You
ng 1
891
Cai
llete
t 189
7P
faun
dler
189
7M
orle
y 19
04G
ebha
rdt 1
905
Sm
ith M
enzi
es 1
910
192
7K
nuds
en 1
909
Ege
rton
1917
Ruf
f 191
9V
olm
er 1
921
Hill
192
2S
cott
1924
Ber
nhar
dt 1
925
Poi
ndex
ter 1
925
Rod
ebus
h 19
25V
olm
er19
25Je
nkin
s 19
26M
illar
192
7N
eum
ann
1932
Ped
der 1
933
von
Hal
ban
1935
Bea
ttie
1937
Sch
neid
er 1
944
Dau
phin
ee 1
950
Dou
glas
195
1B
usey
195
3E
rnsb
erge
r 195
5S
pedd
ing
1955
Roe
der
1956
Sug
awar
a 19
62C
arls
on 1
963
Sch
mah
l 196
5M
orgu
lesc
u 19
66A
mbr
ose
1972
Sch
oumlnhe
rr 1
981
Trip
le p
oint
Nor
mal
boi
ling
poin
tC
ritic
al p
oint
Fi
gure
1 E
xper
imen
tal v
apor
pre
ssur
e da
ta fo
r mer
cury
5
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
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[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
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36
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3] of ia PA 1968
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at
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37
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[54] micron range
[55] ure of the
[56] mercury
[57]
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13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
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t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
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7
[75]
[76] 0degC (in German) Ann
1925
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[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
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(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
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[104] Neale FE Cusack NE Thermoelectric power near the critical point of expanded fluid mercury J Phys F Metal Phys 9(1) 85-94 1979
[79] Rodebush WH Dixon AL The vapor pressures of metals a new experimental method PhyRev 26 851-858 1
[80] Roeder A Morawietz W Investigations on the occurrence of compound molecules in the vapof potassium-merc
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[87] Spedding FH Dye JL The vapor pressure of mercury at 250-360deg J Phys Chem 59 581-1955
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Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Tabl
e 1
Sum
mar
y of
ava
ilabl
e da
ta fo
r the
vap
or p
ress
ure
of m
ercu
ry R
efer
ence
s in
bold
face
indi
cate
prim
ary
data
sets
(see
text
)
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
A
mbr
ose
[18]
19
72
ebul
liom
eter
11
3 41
7-77
1 le
ss th
an 0
03
gre
ates
t at l
owes
t T
Bea
ttie
[28]
19
37
boili
ng tu
be42
623-
636
003
B
ernh
ardt
[41]
19
25
3 st
atic
met
hods
27
69
4-17
06
varie
s fro
m 2
to gt
15
Bes
sel-H
agen
[42]
18
81
Toumlpl
er v
acuu
m p
ump
2 27
3-29
3 gt2
0 B
urlin
gam
e [4
3]
1968
tra
nspi
ratio
n 38
34
4-40
9 4
Bus
ey [4
4]
1953
de
rived
from
cal
oric
pro
perti
es
24
234-
750
varie
s fro
m 0
2 to
35
at l
owes
t T
Cai
llete
t [45
] 19
00
Bou
rdon
man
omet
er
11
673-
1154
va
ries f
rom
1 to
7
Cal
lend
ar [4
6]
1891
M
eyer
tube
2
630
02
Cam
men
ga [4
7]
1969
ef
fusi
on
grap
hica
l res
ults
27
3-32
5
Car
lson
[48]
19
63
effu
sion
9
299-
549
varie
s fro
m 3
to gt
20
Dau
phin
ee [4
9 5
0]
1950
195
1 tra
nspi
ratio
n 18
30
5-45
5 5
Dou
glas
[51]
19
51
deriv
ed fr
om c
alor
ic p
rope
rties
30
23
4-77
3 va
ries f
rom
00
3 (a
t nor
mal
boi
ling
poin
t) to
15
at l
owes
t T
Dur
rans
[52]
19
20
give
s tab
le a
ttrib
uted
to S
mith
an
d M
enzi
es[3
9]
4627
3-72
3
Eger
ton
[53]
19
17
effu
sion
27
28
9-30
9 5
Ern
sber
ger
[54]
19
55pi
ston
man
omet
er18
285-
327
1G
alch
enko
[55]
19
78
stat
ic m
etho
d gr
aphi
cal r
esul
ts
523-
723
3 G
alch
enko
[56]
19
84
atom
ic a
bsor
ptio
n co
rrel
atin
g eq
uatio
n on
ly
723-
873
3
Geb
hard
t [57
] 19
05
boili
ng tu
be
9 40
3-48
3 8
Hab
er [3
7]
1914
vi
brat
ing
quar
tz fi
lam
ent
1 29
3 2
Hag
en [5
8]
1882
di
ffer
entia
l pre
ssur
e 5
273-
473
gt20
Hen
sel [
59]
1966
el
ectri
cal r
esis
tanc
e gr
aphi
cal r
esul
ts
1073
-crit
ical
no
t ava
ilabl
e H
ertz
[35]
18
82
stat
ic a
bsol
ute
man
omet
er
9 36
3-48
0 5
Hey
cock
[60]
19
13
not a
vaila
ble
1 63
0 0
2 H
ilden
bran
d [6
1]
1964
to
rsio
n-ef
fusi
on
6 29
5-33
2 5
Hill
[62]
19
22
radi
omet
er p
rinci
ple
19
27
2-30
8 30
H
ubba
rd [6
3]
1982
st
atic
gr
aphi
cal r
esul
ts
742-
1271
no
t ava
ilabl
e Je
nkin
s [64
] 19
26
isot
enis
cope
21
47
9-67
1 0
1 to
gt20
K
ahlb
aum
[65]
18
94
ebul
liom
eter
43
39
3-49
3 gt1
0 K
nuds
en [6
6]
1909
ef
fusi
on
10
273-
324
varie
s fro
m 5
to 1
0 K
nuds
en [6
7]
1910
ra
diom
eter
prin
cipl
e 7
263-
298
varie
s fro
m 5
to 1
0
6
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
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[27] g point of tin and the boiling point of mercury with a description of a
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[30]
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an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
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hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
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at
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[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
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[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
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37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
[53] cadmium and mercury Phil Mag 33(193) 33-48
[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
[59] ohen Drucken Ber Bunsenges Phys Chem 70(910) 1154-1160 1966
13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
[65] 4
t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
[52] Durrans TH A treatise on distillation Perfumery and Essential Oil Record 11S 154-198 1920Egerton AC The vapour pressure of zinc1917 Ernsberger FM Pitman HW New absolute manometer for vapor pressures in theRev Sci Instrum 26(6) 584-589 1955 Galchenko IE Pelevin OV Sokolov AM Determination of the partial vapor pressvolatile component by the static method Industrial Laboratory 44(12) 1699-1700 1978 Galchenko IE Pelevin OV Sokolov AM Determination of the vapor pressure ofover melts in the Hg-Cd-Te system Inorganic Materials 20(7) 952-955 1984 Gebhardt A Uumlber den Dampfdruck von Quecksilber und Natrium Ber Dtsch Phys Ges 7 184-185 1905 HagenPhys Chem 16 610-618 1882 Hensel F Franck EU Elektrische Leitfaumlhigkeit und Dichte von uumlberkritischem gasfoumlrmigem Quecksilber unter h
[60] Heycock CT Lamplough FEE The boiling points of mercury cadmium zinc potassium and sodium Proc Chem Soc 28 3-4 19
[61] Hildenbrand DL Hall WF Ju F Potter ND Vapor pressures and vapor thermodynamic properties of some lithium and magnesium halides J C
[62] Hill CF Measurement of mercury vapor pressure by means of the Knudsen pressure gauge PhyRev 20 259-266 1922
[63] Hubbard SR Ross RG Slope anomaly in the vapour pressure curve of Hg Nature 295 6683 1982 Jenkins CHM The determodified manometric method Proc R Soc London A 110(754) 456-463 1926 Kahlbaum GWA Studies of vapor pressure measurements (in German) Z Phys Chem 13 14-55 189
[66] Knudsen M Experimental determination of the pressure of saturated mercury vapors at 0degC and ahigher temperatures (in German) Ann Phys 29 179-193 1909 Knudsen M An absolute manometer (in German) Ann Phys 32(4) 89
[68] Kordes E Raaz F Aufnahme von Siedediagrammen binaumlrer hochsiedender Fluumlssigkeitsgemische Z Anorg Allg Chem 181 225-236 1929
[69] Mayer H On a new method for measurements of the lowest vapor pressures the vapor pressuresof mercury and potassium III Communicati1930 McLeod FRS On the pressuthe Meeting of the British Association for the Advancement of Science 443-444 1883 Millar RW The vapor pressures of potassium amalgams J Am Chem Soc 49 3003-3010 1927
[72] Morley EW On the vapour-pressure of mercury at ordinary temperatures Phil Mag 7 662-661904
[73] Murgulescu IG Topor L Vapour pressure and molecular association of NaCl NaBr vapoursRev Roum Chim 11 1353-1360 1966
[74] Neumann K Voumllker E A torsion balance method for measurements of lowest vapor pressures(in German) Z Phys Chem 161 33-45 1932 Pedder JS Barratt S The determination of the vapour pressures of amalgams by a dynamicmethod J Chem Soc (London) 537-546 1933 Pfaundler L On the tension of mercury vapor in the interval 0degC to 10Phys Chem 63(3) 36-43 1897
[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
or ury melts (in German) Z f Elektrochemie 60 431-454 1956
(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
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1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Tabl
e 1
Con
tinue
d
Firs
t Aut
hor
Yea
r M
etho
d N
o p
ts
T ra
nge
K
Est
imat
ed u
ncer
tain
ty
K
orde
s [68
] 19
29
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 2
630-
632
4
May
er [6
9]
1930
ef
fusi
on
82
261-
298
5 e
xcep
t gre
ater
at T
lt270
M
cLeo
d [7
0]
1883
tra
nspi
ratio
n 1
293
gt20
Men
zies
[39
40]
19
101
927
isot
enis
cope
4639
5-70
80
5M
illar
[71]
19
27
isot
enis
cope
6
468-
614
2 M
orle
y [7
2]
1904
tra
nspi
ratio
n 6
289-
343
varie
s fro
m 8
to gt
20
Mur
gule
scu
[73]
19
66
quas
i-sta
tic
9 30
1-54
9 3
Neu
man
n [7
4]
1932
to
rsio
n ba
lanc
e 19
29
0-34
4 6
Pedd
er [7
5]
1933
tra
nspi
ratio
n 3
559-
573
2 Pf
aund
ler [
76]
1897
ga
s sat
urat
ion
3 28
8-37
2 12
Po
inde
xter
[77]
19
25
ioni
zatio
n ga
ge
17
235-
293
5-20
gre
ates
t at l
owes
t T
Raa
be [7
8]
2003
co
mpu
ter s
imul
atio
n 20
40
8-15
75
varie
s fro
m 0
5 to
gt20
R
amsa
y [3
6]
1886
is
oten
isco
pe
13
495-
721
varie
s fro
m 0
3 to
10
at h
ighe
st T
R
egna
ult [
33]
1862
is
oten
isco
pe
29
297-
785
~6 fo
r Tgt4
00 m
uch
high
er fo
r low
er T
R
odeb
ush
[79]
19
25
quas
i-sta
tic
7 44
4-47
6 1
Roe
der [
80]
1956
qu
artz
spira
l man
omet
er
7 41
3-61
4 2
Ruf
f [81
] 19
19
tem
pera
ture
scan
ning
ev
apor
atio
n m
etho
d 12
478-
630
gt20
Schm
ahl [
82]
1965
st
atic
met
hod
43
412-
640
15
Schn
eide
r [83
] 19
44
gas s
atur
atio
n 23
48
4-57
5 10
Sc
houmlnh
err
[84]
19
81el
ectri
cal c
ondu
ctiv
ity13
1052
-173
53
Scot
t [85
] 19
24
vibr
atin
g qu
artz
fila
men
t 1
293
2 Sh
pilrsquor
ain
[86]
19
71
ebul
liom
eter
50
55
4-88
3 0
6 to
08
Sped
ding
[87]
19
55is
oten
isco
pe13
534-
630
003
Stoc
k [8
8]
1929
tra
nspi
ratio
n 3
253-
283
20
Suga
war
a [9
] 19
62
stat
ic m
etho
d 14
60
2-93
0 2
van
der P
laat
s [89
] 18
86
trans
pira
tion
26
273-
358
V
illie
rs [9
0]
1913
eb
ullio
met
er
12
333-
373
6 V
olm
er [9
1]
1925
ef
fusi
on
10
303-
313
3 vo
n H
alba
n [9
2]
1935
re
sona
nce
light
abs
orpt
ion
1
255
7 Y
oung
[93]
18
91
stat
ic
11
457-
718
2
Excl
udes
poi
nts b
elow
the
tripl
e po
int
7
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
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[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
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hem Phys 40(10) 2882-2890 1964 s
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1925
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(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
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ture
[91] essures of solid and liquid benzophenone between 0deg und
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[94] 35(9) 1065-1067 1913
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thod f lishing ra onal vap re e Cryogen s 14 63[1 gner ers J P termann vapo re measurements a ratio
our-p equation r oxyge Th 8(11) 1 9-1060[1 gner e mathem isch stat ethode zum Aufstellen thermodynamischer
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[1 mon rties and vapor pressure equation for alkanes 2n+2 ers f rough n= J Phys ef D
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lliom Chem En Data 4 200[1 vey emmon EW Corre the v ssure of avy wat trip
nt to cal point Phys C Data 173-181 002 [1 gner szlig A Int ational equations for the saturation properties of ordinary water
stanc ed Accor ng to the nal ture Scal of 1990 hema 22 7 1993
[1 gner szlig A Th APWS F n 19 e thermodynamic properties of inary bstance r genera tific hys Che Ref Da 3872
[1 g M ajjar H method lating ending v our pres o loperatures using therm data va ure equations for some -alkanes atur
ow th l boiling int Che ci 2 3-11 19 [1 ner-R A nonlin r regress is fo ing low-t peratur essu
enth vaporiza on appli geran Thermo ys 17(6 85[1 hr P r BN C DATA the fund ental p nstan
2 R Phys 77 ) 1-107[1 se M NIST-JA AF The cal T Phys Ch m Ref D ogra
9 F ition 19 [1 itin EB Lebedeva EG Paukov IE The heat capacity of me ry in th 300 K
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ersity[13 ley J ng W Osc Row DIADE DIPP tion a
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[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
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Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
The Knudsen effusion method is a type of vapor pressure measurement classified as a
dynamic method In this type of experiment a steady rate of evaporation through an orifice
into a vacuum is established and pressure is calculated from the flow rate through the orifice
by use of kinetic theory This method is applicable at very low pressures (below 01 kPa) but
generally has high uncertainties
As indicated in Table 1 many measurements have been made on the vapor pressure
of mercury However only a limited number of these are comprehensive and have
uncertainty levels of one percent or less These sets have been identified as primary data sets
in our work and are indicated by boldface type in Table 1 In general the most accurate
measurements were those made with ebulliometric methods Ambrose and Sprake [18] used
an ebulliometric technique for their measurements from 380 K to 771 K These data have an
uncertainty of about 003 or lower with the largest uncertainty at the lowest temperatures
Beattie et al [28] very accurately determined the boiling point of mercury over the
temperature range 623 K to 636 K Spedding and Dye [87] used an isoteniscope to measure
the vapor pressure over the range 534 K to 630 K with uncertainties on the order of 003
except at the lowest temperatures where they are larger Menzies [40 94] used an
isoteniscope at temperatures from 395 K to 708 K but these data show more scatter and have
larger uncertainties than the sets mentioned above however the uncertainties are still less
than 05 Shpilrsquorain and Nikanorov [86] used an ebulliometric method extending from 554
K to 883 K Their data are more consistent with the measurements of Ambrose and Sprake
[18] in their region of overlap than are other high temperature sets such as those by
Sugawara et al [9] Bernhardt [41] or Cailletet et al [45] and thus were selected as the
primary data for the high temperature region from about 700 K to 900 K In addition
although the uncertainty is higher than 1 we have selected the data of Schoumlnherr and
Hensel [84] for the highest temperature region 1052 K to 1735 K This data set was obtained
by observing changes in the electrical conductivity At fixed pressures the temperature was
raised and when a discontinuity was observed this was taken as an indication of phase
change
All of the sets mentioned so far are for temperatures greater than 380 K At lower
temperatures the measurements are much more uncertain and display significant scatter In
the low temperature range we considered the measurements of Ernsberger and Pitman [54]
8
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
to be the most accurate These measurements were made with an absolute manometer
method with uncertainties on the order of 1 and they cover the temperature range 285 K
to 327 K This data set has been adopted in the metrology community for use in precision
manometry and has been described as reliable and confirmed by heat capacity measurements
[95] The reliability and thermodynamic consistency of these data will be discussed in more
detail in a later section of this document
The end points of the vapor pressure curve for stable vapor-liquid equilibrium are the
triple point and the critical point Metastable points may be obtained at points below the
triple point In principle the three phase-boundary curves that meet at the gas-liquid-solid
triple point of a pure substance continue beyond this intersection so that the phase equilibria
become metastable relative to the third phase which is absolutely stable Vapor-liquid
equilibrium along the vapor pressure curve continued below the triple point becomes
metastable relative to the solid phase and vapor-solid equilibrium along the sublimation
pressure curve continued above the triple point becomes metastable relative to the liquid
phase Although the former has been realized in experiments [96] metastable phase
equilibria are one of the least investigated phenomena of the behavior of matter Their
existence in principle is mentioned here because three datasets in the present collection
report mercury vapor pressure data at temperatures below the triple point Poindexter [77]
Stock and Zimmermann [88] and von Halban [92] The farthest reaching data below the
triple point temperature are the results of Poindexter covering a range from 194 K to 293 K
However in this work we restrict our study to points above the triple point although all
points are tabulated in Appendix A
The triple point of mercury has been designated as a fixed point of the ITS-90 [30]
temperature scale with a value of 2343156 K The critical point has been measured by
several investigators these values are listed in Table 2 along with uncertainty estimates
provided by the authors One of the first measurements of the critical point was made by
Koenigsberger [97] in 1912 who made visual observations in a quartz tube and reported the
critical temperature of mercury to be near 1270 degC (1543 K) This measurement was later
criticized by Menzies [94] who reported that the critical temperature was at least 1275 degC
(1548 K) Another early determination was that of Bernhardt [41] who extrapolated his vapor
pressure observations and used Benderrsquos [98] value of 1650 degC (1923 K) for the critical
9
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
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[27] g point of tin and the boiling point of mercury with a description of a
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[30]
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an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
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at
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[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
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[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
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37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
[53] cadmium and mercury Phil Mag 33(193) 33-48
[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
[59] ohen Drucken Ber Bunsenges Phys Chem 70(910) 1154-1160 1966
13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
[65] 4
t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
[52] Durrans TH A treatise on distillation Perfumery and Essential Oil Record 11S 154-198 1920Egerton AC The vapour pressure of zinc1917 Ernsberger FM Pitman HW New absolute manometer for vapor pressures in theRev Sci Instrum 26(6) 584-589 1955 Galchenko IE Pelevin OV Sokolov AM Determination of the partial vapor pressvolatile component by the static method Industrial Laboratory 44(12) 1699-1700 1978 Galchenko IE Pelevin OV Sokolov AM Determination of the vapor pressure ofover melts in the Hg-Cd-Te system Inorganic Materials 20(7) 952-955 1984 Gebhardt A Uumlber den Dampfdruck von Quecksilber und Natrium Ber Dtsch Phys Ges 7 184-185 1905 HagenPhys Chem 16 610-618 1882 Hensel F Franck EU Elektrische Leitfaumlhigkeit und Dichte von uumlberkritischem gasfoumlrmigem Quecksilber unter h
[60] Heycock CT Lamplough FEE The boiling points of mercury cadmium zinc potassium and sodium Proc Chem Soc 28 3-4 19
[61] Hildenbrand DL Hall WF Ju F Potter ND Vapor pressures and vapor thermodynamic properties of some lithium and magnesium halides J C
[62] Hill CF Measurement of mercury vapor pressure by means of the Knudsen pressure gauge PhyRev 20 259-266 1922
[63] Hubbard SR Ross RG Slope anomaly in the vapour pressure curve of Hg Nature 295 6683 1982 Jenkins CHM The determodified manometric method Proc R Soc London A 110(754) 456-463 1926 Kahlbaum GWA Studies of vapor pressure measurements (in German) Z Phys Chem 13 14-55 189
[66] Knudsen M Experimental determination of the pressure of saturated mercury vapors at 0degC and ahigher temperatures (in German) Ann Phys 29 179-193 1909 Knudsen M An absolute manometer (in German) Ann Phys 32(4) 89
[68] Kordes E Raaz F Aufnahme von Siedediagrammen binaumlrer hochsiedender Fluumlssigkeitsgemische Z Anorg Allg Chem 181 225-236 1929
[69] Mayer H On a new method for measurements of the lowest vapor pressures the vapor pressuresof mercury and potassium III Communicati1930 McLeod FRS On the pressuthe Meeting of the British Association for the Advancement of Science 443-444 1883 Millar RW The vapor pressures of potassium amalgams J Am Chem Soc 49 3003-3010 1927
[72] Morley EW On the vapour-pressure of mercury at ordinary temperatures Phil Mag 7 662-661904
[73] Murgulescu IG Topor L Vapour pressure and molecular association of NaCl NaBr vapoursRev Roum Chim 11 1353-1360 1966
[74] Neumann K Voumllker E A torsion balance method for measurements of lowest vapor pressures(in German) Z Phys Chem 161 33-45 1932 Pedder JS Barratt S The determination of the vapour pressures of amalgams by a dynamicmethod J Chem Soc (London) 537-546 1933 Pfaundler L On the tension of mercury vapor in the interval 0degC to 10Phys Chem 63(3) 36-43 1897
[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
or ury melts (in German) Z f Elektrochemie 60 431-454 1956
(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
[96] Debenedetti Metastable Liquids Concepts and Principles Princeton NJ Princeton
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Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
temperature while estimating the critical pressure to be in the range 2942 to 3432 MPa
Later Birch [99] determined the critical point by observing the changes in electrical
resistance as a function of temperature at constant pressure The review paper of Mathews
[100] adopted Birchrsquos values for the critical point Ambrose [101] and also Vargaftik et al
[8] instead selected the value obtained by Franck and Hensel [102] also obtained from
studies of changes in electrical resistance Kikoin and Senchenkov [103] used electrical
conductivity experiments to locate the critical point Neale and Cusack [104] observed
changes in the Seebeck voltage while Goumltzlaff [13] analyzed isochoric and isobaric PVT
data extrapolated to the saturation boundary Most recently Kozhevnikov et al [105]
observed changes in the speed of sound along isobars as a function of temperature to
determine the critical point The value by Bernhardt [41] is too high both in pressure and in
temperature The critical temperature of Franck and Hensel [102] agrees very well with that
obtained by Kozhevnikov et al [105] while the critical pressure of Goumltzlaff [13] agrees very
well with that of Kozhevnikov et al [105] In this work we adopted the critical point of
Kozhevnikov et al [105]
Table 2 The critical temperature and pressure of mercury
First Author Year Tc (K) pc (MPa) Koenigsberger [97] 1912 ~1543 Menzies [94] 1913 gt1548 Bender [98] 1915 1923 Meyer [106] 1921 1747 Bernhardt [41] 1925 1923 2942 - 3432 Birch [99] 1932 1733 plusmn 20 161 plusmn 5 Franck [59 102] 1966 176315 plusmn 15 151 plusmn 3 Kikoin [103] 1967 1753 plusmn 10 152 plusmn 1 Neale [104] 1979 1768 plusmn 8 1675 plusmn 25 Hubbard [107] 1983 1750 172 Goumltzlaff [13] 1988 1751 plusmn 1 1673 plusmn 02 Kozhevnikov [105] 1996 1764 plusmn 1 167 plusmn 3
Uncertainties are expressed in kelvins and megapascals for the temperature and pressure respectively
10
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
3 Correlation Development
Numerous expressions have been used to represent the vapor pressure of a pure fluid
many are reviewed in Růžička and Majer [108] Equations of the general form
2( ) ( ) i
c c ii
ln p p T T aτ= sum (1)
where τ = 1-TTc are attributed to Wagner [109-112] and have been used successfully to
represent the vapor pressures of a wide variety of fluids Lemmon and Goodwin [113] used
the Wagner form with exponents (1 15 25 and 5) to represent the vapor pressures of
normal alkanes up to C36 This form which we will call Wagner 25-5 is one of the most
widely used forms along with the equation with exponents (1 15 3 and 6) [109 110]
which we call Wagner 3-6 The 25-5 form has emerged as the generally preferred form
[114] When the data set is extensive and of high quality other forms with alternative sets of
exponents with additional terms have been used For example a Wagner equation with
exponents (1 15 2 25 and 55) was used to represent the vapor pressure of acetonitrile
[115] and another variant of the Wagner equation with exponents (1 189 2 3 and 36)
was used to represent the vapor pressure of heavy water [116] from the triple point to the
critical point to within the experimental scatter of the measurements The International
Association for the Properties of Water and Steam (IAPWS) formulation for the vapor
pressure of water [117 118] uses a six-term Wagner equation with exponents of (1 15 3
35 4 and 75)
Since there is a lack of high-quality experimental vapor-pressure data in the low
temperature region (T lt 285 K) liquid heat capacity measurements at low temperatures can
be used to supplement the vapor-pressure data [108 114 119] This permits the
simultaneous regression of heat capacity and vapor-pressure data to determine the
coefficients of a vapor pressure equation that is valid down to the triple point An alternative
method is to use an expression involving enthalpies of vaporization in addition to vapor-
pressure data [120] Both of these approaches can be used to ensure that the vapor pressure is
thermodynamically consistent with other thermodynamic data
King and Al-Najjar [119] related heat capacity and vapor pressure using
11
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
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36
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13
hem Phys 40(10) 2882-2890 1964 s
82-
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t
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1925
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[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
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s 925
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(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
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[85] ur pressures of cesium and rubidium and a calculation of
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ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
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4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
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7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
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[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
02 ln L
p psat C C Gd pd TdT dT R
minus minus⎛ ⎞ =⎜ ⎟⎝ ⎠
(2)
K) psat is the vapor
ressure and G represents vapor phase nonidealities and is given by
where Cpdeg and CpL are the heat capacities at constant pressure of the ideal gas and the
saturated liquid R is the molar gas constant [121] R=8314 472 J(mol
p
( )22
2 22 sat satLsat L
dp d pdVd B dBG T p B VdT dT dT dT dT
⎛ ⎞⎛ ⎞= + minus + minus⎜ ⎟⎜ ⎟⎝ ⎠⎝ ⎠
(3)
l
rence in
n of eq
of
above The smoothed heat capacity data from these two sources are listed in
In this expression B is the second virial coefficient and VL is the molar volume of the liquid
We restrict the use of this equation to temperatures lower than 270 K where vapor pressures
are on the order of 10-5 kPa In this region we treat the gas phase as ideal so that the G term
may be neglected (For example we applied equations in Douglas et al [51] for the viria
coefficients liquid volumes heat capacities vapor pressures and their derivatives and
estimated that the magnitude of the term G at 270 K relative to the heat capacity diffe
eq (2) is on the order 10-4 ) Assuming that mercury can be considered as an ideal
monatomic gas for these low pressures the ideal gas heat capacity for mercury is Cpdeg = 5R2
[122] With these assumptions after the derivatives of the vapor pressure in eq (2) are taken
analytically incorporating the specific form of the vapor pressure correlation functio
(1) one obtains the simple expression (5R2 minus CpL)R = (TTc)Σai(i2)(i2 minus 1)ti2-1
Busey and Giauque [44] measured the heat capacity Cp of mercury from 15 to 330 K
with estimated uncertainties of 01 Amitin et al [123] also measured the heat capacity
mercury at temperatures from 5 K to 300 K with an estimated uncertainty of 1 The
smoothed data over the temperature range 234 K to 270 K from these two sources were
identified as primary data for use in the regression in addition to the primary vapor pressure
data discussed
Appendix B
For our analysis of both psat and Cp experimental data all temperatures were first
converted to the ITS-90 scale Data taken prior to 1927 were converted to ITS-90 assuming
12
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
[26] Dalton J Experimental Essays II On the force of steam or vapour from water and various other liquids both in a vacuum and in air Mem Proc - Manchester Lit Philos Soc 5(2) 550-574
[27] g point of tin and the boiling point of mercury with a description of a
[28] mperature
[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
Oxford UK 1987
[34] mpfs bei verschiedenen Temperaturen
[35] (in German) Ann Phys Chem 17 193-200 1882
an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
[45] Colardeau E Riviegravere C Recherches sur les tensions de le vapeur de mercure
at
[47] he determination of high precision vapour pressure of mercury and its
tional Conference on Calorimetry and Thermodynamics Warsaw
[48] cells J Chem Phys 38(11) 2725-2735 1963
lumbia Vancouver Canada 1950
1801 Crichton J On the freezinself-registering thermometer Phil Mag (March) 147-148 1803 Beattie JA Blaisdell BE Kaminsky J An experimental study of the absolute tescale IV Reproducibility of the mercury boiling point The effect of pressure on the mercury boiling point Proc Am Acad Arts Sci 71 375-385 1937 Hall JA Barber CR The Internation1(4) 81-85 1950 Preston-Thomas H The international temperature scale of 1990 (ITS-90) Metrologia 27 3-10 1990
[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
[32] Preston-Thomas H The international practical temperature scale of 1968 amended edition of 1975 Metrologia 12 7-17 1976
[33] Regnault V Forces eacutelastiques des vapeurs Mem Acad Sci Inst Fr 26 506-525 1862 Avogadro A Ueber die Spannkraft des QuecksilberdaPogg Ann 27 60-80 1833 Hertz H On the pressure of saturated mercury
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
that the older data were on the International Temperature Scale of 1927 although we realize
this introduces additional uncertainties Except for the data of Menzies [40] all primary data
were measured after 1927 The temperatures of the data of Menzies were first converted to
the 1948 temperature scale
by use of the procedure given by Douglas et al [51] and then
iple
t
e
t the
g the
tive
its were considered outliers and were not included in the statistics and final
were converted to ITS-90
We regressed the primary data set to three different Wagner-type expressions the 3-
6 the 25-5 and a variable exponent expression where the exponents were selected from a
bank of terms by use of a simulated annealing procedure [124 125] Simulated annealing is
an optimization technique that can be used in complex problems where there may be mult
local minima It is a combinatorial method that does not require derivatives and does no
depend upon ldquotraveling downhillrdquo it also is relatively easy to implement An example
program using the simulated annealing to solve the Traveling Salesman Problem is given in
the book by Press et al [125] In this work the search space contained a bank of terms where
the bank contained exponents with powers of τ in increments of 05 with terms up to τ12 W
followed the recommendation of Harvey and Lemmon [116] and required the equation to
contain terms of order 1 189 and 2 based on theoretical considerations on the behavior
near the critical point The simulated annealing algorithm was used to determine the optimal
terms from the bank of terms We implemented a Lundy and Mees [126] annealing schedule
similar to that of earlier work [127] During the regression one can treat the critical pressure
as a variable to be determined in the regression or it can be fixed Due to concerns abou
quality and amount of experimental data in the temperature range 930 K to 1764 K we
adopted the critical point of Kozhevnikov et al [105] rather than determining it by fitting
experimental data The minimization was done with orthogonal distance regression usin
NIST statistical package ODRPACK [128] For the regression the data were weighted
according to their estimated uncertainty (u) with weights of 1u2 In addition the vapor
pressure data were given a relative weight factor of one and the heat capacity data a rela
weight factor of 002 Points that deviated by more than three standard deviations from
preliminary f
regression
The 25-5 form of the Wagner equation provided a better fit of the primary data set
than the 30-6 form further improvement resulted from the use of the simulated annealing
13
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
algorithm Upon closer inspection we noted that although one could reasonably reproduce
the numerical value of the heat capacity it was not possible to reproduce well the slope o
the saturated liquid heat capacity near the triple point without degrading the fit in other
regions We note that the liquid heat capacity at saturation of mercury as a function of
temperature displays an interesting behaviormdasha distinct minimum in the curve is observed
below the normal boiling point as shown in Figure 2 Douglas et al [51] noted that other
liquid metals such as sodium and potassium also exhibit this behavior Among nonmetals we
observe that water displays this feature however it is not observed in simple hydrocarb
such as linear alkanes In order to simultaneously fit the vapor pressure and liquid heat
capacity data and have the correct behavior of the slope of the heat capacity as a fun
temperature along the saturation boundary we increased the number of terms in the
regression
f
ons
ction of
from 5 to 6 and used the simulated annealing algorithm to obtain our final
quation
e
( )189 2 8 85 91 2 3 4 5 6( ) ( )c cln p p T T a a a a a aτ τ τ τ τ τ= + + + + + (4)
d
r
21] R
= 8314 472 J(molK) and the relative atomic mass [129] of mercury 20059 gmol
The regressed coefficients and their standard deviations are given in Table 3a and fixe
parameters for eq (4) are given in Table 3b Table 4 gives sample values of the vapo
pressure calculated from eq (4) over the temperature range 27315 to 33315 K For
validation of computer code more digits than are statistically meaningful are given For the
calibration community we also have included in Table 4 the density of saturated mercury
vapor in moles per liter and nanograms per milliliter obtained assuming the ideal gas law
applies ρ = p(RT) We use the currently accepted values of the molar gas constant [1
14
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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Physical Chemistry Science and Engineering ed Prausnitz
[8] and
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e thermodynamic
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sport Health elate s for amp Inorg ic Che Grawssion 784 p
[13 aftik les on e The l Pro Liquids nd Ga ork ted Pr 2nd e
[13 ley R al com unic ber M ham Yo g Uni vo Ut2 20
[13 e E w DN Evalu ermo unctions rom eq onstans Far 2 539- 47 1
[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
24 [142] olmer M Estermann I On the evaporation coeff of solid a d liquid m (in
erman) Zeitschr f Physik 7 1-12 1921 [143] witt FB method of determ e llic vapou an
perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
270
272
274
276
278
280
282
284
286
288
200 300 400 500 600 700 800
Temperature K
Cp
J(m
olmiddotK
)
Busey Giauque 1953
Amitin et al 1979
Triple point
Normal boiling point
Figure 2 Temperature dependence of the heat capacity of saturated liquid mercury
15
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
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[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
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hem Phys 40(10) 2882-2890 1964 s
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(in German) Z
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ture
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0] Lange NA ed Handbook of ChemD Atomi ts ements P
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[131] Washburn EW ed International Critical Tables of Numerical Data Physics Chemistry and chnology e III McGraw-Hill New York 1928
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[13 Kor physic Prop bank ttpww cheric
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Rato3] KDB
2004 ea Thermo al erties Data (KDB) h w orgkdb Korea
ersity[13 ley J ng W Osc Row DIADE DIPP tion a
Eval nager 70 oun ity Prov UT 2[135] Yaws CL l Prop rties H Phys modyna ics En l
sport Health elate s for amp Inorg ic Che Grawssion 784 p
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[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
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search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
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400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Table 3a Fitted values of the parameters in eq (4) and their standard deviations
i ai Std dev 1 - 4576 183 68 00472 2 -1407 262 77 08448 3 2362 635 41 08204 4 -31088 998 5 13439 5 58018 395 9 24999 6 -27630 454 6 11798
Table 3b Fixed parameters in eq (4)
Tc (K) pc (MPa)
1764 167
16
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
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[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
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36
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3] of ia PA 1968
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37
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[54] micron range
[55] ure of the
[56] mercury
[57]
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13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
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t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
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7
[75]
[76] 0degC (in German) Ann
1925
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[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
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(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
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ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
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temperature range 0-2000degC and pressure range of 200-5000 Atm Phys Metals Metallog 24(5) 74-89 1967
[104] Neale FE Cusack NE Thermoelectric power near the critical point of expanded fluid mercury J Phys F Metal Phys 9(1) 85-94 1979
[79] Rodebush WH Dixon AL The vapor pressures of metals a new experimental method PhyRev 26 851-858 1
[80] Roeder A Morawietz W Investigations on the occurrence of compound molecules in the vapof potassium-merc
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[147] Zaitsau DH Verevkiapor pres d env
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Tabl
e 4
Vap
or p
ress
ure
of m
ercu
ry c
alcu
late
d w
ith e
q (4
) fro
m 2
73 K
to 3
33 K
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
T K
t
degC
p M
Pa
Idea
l gas
de
nsity
dagger mol
L
Idea
l gas
de
nsity
dagger ng
mL
273
15
0
269
88291
0-81
1883
371
0-82
3836
8430
415
314
2590
451
0-71
6841
851
0-733
783
0627
415
12
9793
921
0-81
3070
881
0-82
6218
8730
515
324
6114
951
0-71
8175
811
0-736
458
8527
515
23
2867
201
0-81
4366
751
0-82
8818
2630
615
334
9904
731
0-71
9605
271
0-739
326
2027
615
33
6231
291
0-81
5779
901
0-83
1652
8930
715
345
3977
701
0-72
1136
311
0-742
397
3227
715
43
9911
181
0-81
7319
891
0-83
4741
9630
815
355
8352
831
0-72
2775
351
0-745
685
0827
815
54
3933
761
0-81
8996
981
0-83
8106
0530
915
366
3050
241
0-72
4529
171
0-749
203
0527
915
64
8327
951
0-82
0822
171
0-84
1767
2031
015
376
8091
171
0-72
6404
891
0-752
965
5628
015
75
3124
871
0-82
2807
231
0-84
5749
0331
115
387
3498
131
0-72
8410
041
0-756
987
7028
115
85
8357
981
0-82
4964
771
0-85
0076
8231
215
397
9294
931
0-73
0552
551
0-761
285
3528
215
96
4063
191
0-82
7308
251
0-85
4777
6231
315
408
5506
711
0-73
2840
751
0-765
875
2728
315
107
0279
071
0-82
9852
091
0-85
9880
3131
415
419
2160
051
0-73
5283
441
0-770
775
0628
415
117
7046
981
0-83
2611
691
0-86
5415
7931
515
429
9283
021
0-73
7889
861
0-776
003
2728
515
128
4411
281
0-83
5603
481
0-87
1417
0231
615
431
0690
521
0-64
0669
721
0-781
579
3928
615
139
2419
501
0-83
8845
011
0-87
7919
2031
715
441
1505
801
0-64
3633
241
0-787
523
9128
715
141
0112
251
0-74
2354
981
0-88
4959
8631
815
451
2377
431
0-64
6791
161
0-793
858
3828
815
151
1057
491
0-74
6153
341
0-89
2578
9931
915
461
3308
881
0-65
0154
751
0-710
060
5428
915
161
2083
481
0-75
0261
351
0-810
081
9232
015
471
4303
831
0-65
3735
851
0-710
778
8829
015
171
3196
461
0-75
4701
611
0-810
972
6032
115
481
5366
131
0-65
7546
901
0-711
543
3329
115
181
4403
081
0-75
9498
221
0-811
934
7532
215
491
6499
851
0-66
1600
931
0-712
356
5329
215
191
5710
461
0-76
4676
781
0-812
973
5232
315
501
7709
281
0-66
5911
621
0-713
221
2129
315
201
7126
191
0-77
0264
521
0-814
094
3632
415
511
8998
901
0-67
0493
291
0-714
140
2529
415
211
8658
351
0-77
6290
361
0-815
303
0832
515
522
0373
471
0-67
5360
971
0-715
116
6629
515
222
0315
581
0-78
2785
021
0-816
605
8532
615
532
1837
951
0-68
0530
401
0-716
153
5929
615
232
2107
081
0-78
9781
121
0-818
009
1932
715
542
3397
601
0-68
6018
061
0-717
254
3629
715
242
4042
651
0-79
7313
231
0-819
520
0632
815
552
5057
891
0-69
1841
181
0-718
422
4229
815
252
6132
711
0-71
0541
801
0-721
145
8132
915
562
6824
621
0-69
8017
831
0-719
661
4029
915
262
8388
371
0-71
1413
441
0-722
894
2333
015
572
8703
851
0-61
0456
691
0-620
975
0730
015
273
0821
411
0-71
2350
361
0-724
773
5833
115
583
0701
931
0-61
1150
811
0-622
367
4030
115
283
3444
401
0-71
3356
911
0-726
792
6233
215
593
2825
551
0-61
1886
201
0-623
842
5330
215
293
6270
661
0-71
4437
701
0-728
960
5933
315
603
5081
701
0-61
2665
031
0-625
404
7830
315
303
9314
331
0-71
5597
631
0-731
287
29
dagger A
ssum
es id
eal g
as la
w a
pplie
s
17
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
[26] Dalton J Experimental Essays II On the force of steam or vapour from water and various other liquids both in a vacuum and in air Mem Proc - Manchester Lit Philos Soc 5(2) 550-574
[27] g point of tin and the boiling point of mercury with a description of a
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[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
Oxford UK 1987
[34] mpfs bei verschiedenen Temperaturen
[35] (in German) Ann Phys Chem 17 193-200 1882
an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
[45] Colardeau E Riviegravere C Recherches sur les tensions de le vapeur de mercure
at
[47] he determination of high precision vapour pressure of mercury and its
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lumbia Vancouver Canada 1950
1801 Crichton J On the freezinself-registering thermometer Phil Mag (March) 147-148 1803 Beattie JA Blaisdell BE Kaminsky J An experimental study of the absolute tescale IV Reproducibility of the mercury boiling point The effect of pressure on the mercury boiling point Proc Am Acad Arts Sci 71 375-385 1937 Hall JA Barber CR The Internation1(4) 81-85 1950 Preston-Thomas H The international temperature scale of 1990 (ITS-90) Metrologia 27 3-10 1990
[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
[32] Preston-Thomas H The international practical temperature scale of 1968 amended edition of 1975 Metrologia 12 7-17 1976
[33] Regnault V Forces eacutelastiques des vapeurs Mem Acad Sci Inst Fr 26 506-525 1862 Avogadro A Ueber die Spannkraft des QuecksilberdaPogg Ann 27 60-80 1833 Hertz H On the pressure of saturated mercury
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[39] Smith A Menzies AWC Studies in vapor pressure IV A redetermination of the vapor pressures of mercury from 250deg to 435deg J Am C
[40] Menzies AWC The vapour pressures of liquid mercury Z Phys Chem 130 90-94 192[41] Bernhardt F Saturation pressure of mercury up to 2000 kgcm2 (in German) Phys Z 26(6) 265-
275 1925 [4 Bessel-Hagen E Ueber eine neue Form der Toumlplerschen Quecksilberluftpumpe und einige mit i
angestellte Versuche Ann Phys Chem 12(2) 425-445 1881 [4 Burlingame JW Dilute solutions of mercury in liquid binary alloys PhD Thesis University
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properties of solid liquid and ga809 1953 Cailletet L satureacutee Compt Rend 130 1585-1591 1900
[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
[49] Dauphinee TM The measurement of the vapour pressure of mercury in the intermediate pressure range PhD Thesis University of British Co
37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
[53] cadmium and mercury Phil Mag 33(193) 33-48
[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
[59] ohen Drucken Ber Bunsenges Phys Chem 70(910) 1154-1160 1966
13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
[65] 4
t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
[52] Durrans TH A treatise on distillation Perfumery and Essential Oil Record 11S 154-198 1920Egerton AC The vapour pressure of zinc1917 Ernsberger FM Pitman HW New absolute manometer for vapor pressures in theRev Sci Instrum 26(6) 584-589 1955 Galchenko IE Pelevin OV Sokolov AM Determination of the partial vapor pressvolatile component by the static method Industrial Laboratory 44(12) 1699-1700 1978 Galchenko IE Pelevin OV Sokolov AM Determination of the vapor pressure ofover melts in the Hg-Cd-Te system Inorganic Materials 20(7) 952-955 1984 Gebhardt A Uumlber den Dampfdruck von Quecksilber und Natrium Ber Dtsch Phys Ges 7 184-185 1905 HagenPhys Chem 16 610-618 1882 Hensel F Franck EU Elektrische Leitfaumlhigkeit und Dichte von uumlberkritischem gasfoumlrmigem Quecksilber unter h
[60] Heycock CT Lamplough FEE The boiling points of mercury cadmium zinc potassium and sodium Proc Chem Soc 28 3-4 19
[61] Hildenbrand DL Hall WF Ju F Potter ND Vapor pressures and vapor thermodynamic properties of some lithium and magnesium halides J C
[62] Hill CF Measurement of mercury vapor pressure by means of the Knudsen pressure gauge PhyRev 20 259-266 1922
[63] Hubbard SR Ross RG Slope anomaly in the vapour pressure curve of Hg Nature 295 6683 1982 Jenkins CHM The determodified manometric method Proc R Soc London A 110(754) 456-463 1926 Kahlbaum GWA Studies of vapor pressure measurements (in German) Z Phys Chem 13 14-55 189
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
4 Comparison with Experimental Data
For the 294 vapor pressure points in the primary data set the average absolute
deviation is 014 the bias is minus0028 and the root mean square deviation is 035
where we use the definitions AAD = (100n)Σabs(picalc pi
expt minus 1) BIAS = (100n)
Σ(picalc pi
expt minus 1) and RMS2 = (100n)( Σ(picalc pi
expt minus 1)2 minus ((100n) Σ(picalc pi
expt minus 1))2
where n is the number of points The AAD and RMS for the primary data are given in
Table 5 The normal boiling point calculated by this equation is 6297705 K
Figure 3 compares the primary data set with our correlation eq (4) The data of
Ernsberger and Pitman [54] display substantial scatter but the results are within their
estimated experimental uncertainty of 1 The data of Shpilrsquorain and Nikanorov [86]
also display a fairly high scatter but again it is within their uncertainty estimate (06
to 08 ) The very accurate measurements of Beattie et al [28] are in the vicinity of the
normal boiling point and the correlation eq (4) indicates an uncertainty of 002 at a
coverage factor of 2 The measurements of Spedding and Dye [87] and those of Ambrose
and Sprake [18] also are represented well by our correlation although the lowest
temperature points display larger scatter than at higher temperatures The measurements
of Menzies [39 40] are also represented to within their estimated uncertainty The
highest temperature data of Schoumlnherr and Hensel [84] are represented with an AAD of 1
and a standard deviation of 14 several points are outside of the range of the plot
and are not shown The correlation is valid to the critical point at 1764 K but does not
account for a metal-nonmetal transition [63] in mercury at approximately 1360 K that
results in a change of slope in the vapor pressure curve
18
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
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[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
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36
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[54] micron range
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13
hem Phys 40(10) 2882-2890 1964 s
82-
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t
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7
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1925
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[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
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(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
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[85] ur pressures of cesium and rubidium and a calculation of
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ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
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thod f lishing ra onal vap re e Cryogen s 14 63[1 gner ers J P termann vapo re measurements a ratio
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[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
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Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Table 5 Summary of comparisons of the correlation with the primary data for the vapor
pressure of mercury
First author No pts
T range K
Estimated uncertainty AAD
RMS
Ambrose [18] 113 417-771 less than 003 greatest at lowest T 002 006 Beattie [28] 42 623-636 003 001 001 Ernsberger [54] 18 285-327 1 033 035 Menzies [39 40] 46 395-708 05 014 020 Schoumlnherr [84] 13 1052-
1735 3 106 142
Shpilrsquorain [86] 50 554-883 06-08 025 029 Spedding [87] 13 534-630 003 005 006
Two outliers at 380 K and 400 K were not included in statistics One outlier at 395 K was not included in statistics
-1
-08
-06
-04
-02
0
02
04
06
08
1
200 700 1200 1700Temperature K
100
[(p-p
eq(4
))p
]
Ambrose Sprake 1972 Spedding Dye 1955
Shpilrain Nikanorov 1971 Menzies 19101927
Beattie et al 1937 Ernsberger Pitman 1955
Schoumlnherr Hensel 1981
Figure 3 Deviations between the correlation given in eq (4) and the primary data set
19
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Figure 4 compares selected data not used in the regression (secondary data) with
the correlation eq (4) and Table 6 summarizes comparisons with all secondary data It is
interesting to note that the behavior of the correlation at low temperatures falls in
between the values of Douglas et al [51] and those of Busey and Giauque [44] Both of
these sets were not obtained from direct vapor pressure measurements but rather were
calculated based upon caloric measurements combined with vapor pressure data at higher
temperatures The data of Schmahl et al [82] cover a range of temperature from 412 to
640 K and are in good agreement with the correlation The measurements of Burlingame
[43] and of Dauphinee [4950] were made by use of a transpiration technique with
uncertainties on the order of 4 to 5 and the correlation represents them within this
range of deviations Figure 4 also displays considerably more scatter at both the high and
low temperature ends of the plot
-10
-8
-6
-4
-2
0
2
4
6
8
10
200 400 600 800 1000Temperature K
100
[(p-p
eq(4
))p
]
Douglas et al 1951 Burlingame 1968Busey Giauque 1953 Dauphinee 1951Murgulescu Topor 1966 Schmahl et al 1965Sugawara et al 1962 Volmer Kirchoff 1925Roeder Morawietz 1956 Hildenbrand et al 1964Cailletet et al 1897 Rodebush Dixon 1925Egerton 1917 Poindexter 1925
Figure 4 Deviations between the correlation given in eq (4) and selected secondary data
20
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Table 6 Summary of comparisons of the correlation given in eq (4) with secondary data
for the vapor pressure of mercury
First author No pts T range K
Estimated uncertainty
AAD RMS
Bernhardt [41] 27 694-1706 varies from 2 to gt15 1413 1726 Bessel-Hagen [42] 2 273-293 gt20 9612 250 Burlingame [43] 38 344-409 4 144 192 Busey [44] 24 234-750 varies from 02 to 35 at lowest T 090 103 Cailletet [45] 11 673-1154 varies from 1 to7 397 226 Callendar [46] 2 630 02 017 014 Cammenga [47] graphical results 273-325 Carlson [48] 9 299-549 varies from 3 to gt20 1974 1683 Dauphinee [49 50] 18 305-455 5 214 294 Douglas [51] 30 234-773 var from 003 (at normal boiling
point) to 15 at lowest T 045 054
Durrans [52] 19 290-344 463 306 Egerton [53] 27 289-309 5 699 234 Galchenko [55] graphical results 523-723 3 na na Gebhardt [57] 9 403-483 8 334 403 Haber [37] 1 293 2 184 na Hagen [58] 5 273-473 gt20 5102 5744 Hensel [59] graphical results 1073-critical na na na Hertz [35] 9 363-480 5 450 194 Heycock [60] 1 630 02 021 Na Hildenbrand [61] 6 295-332 5 276 316 Hill [62] 19 272-308 30 2940 438 Hubbard [63] graphical results 742-1271 na na na Jenkins [64] 21 479-671 varies from 01 to gt20 508 567 Kahlbaum [65] 43 393-493 gt10 889 947 Knudsen [66] 10 273-324 varies from 5 to 10 736 167 Knudsen [67] 7 263-298 varies from 5 to 10 712 764 Kordes [68] 2 630-632 4 259 184 Mayer [69] 82 261-298 5 except greater at Tlt270 672 886 McLeod [70] 1 293 gt20 7765 na Millar [71] 6 468-614 2 127 184 Morley [72] 6 289-343 varies from 8 to gt20 1758 1182 Murgulescu [73] 9 301-549 3 141 156 Neumann [74] 19 290-344 6 463 306 Pedder [75] 3 559-573 2 114 094 Pfaundler [76] 3 288-372 12 806 576 Poindexter [77] 17 235-293 gt5-20 greatest at lowest T 2823 2919 Ramsay [36] 13 495-721 varies from 03 to 10 at highest T 323 302 Regnault [33] 29 297-785 ~6 for Tgt400 much higher for
lower T 2474 3403
Rodebush [79] 7 444-476 1 053 054
21
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
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36
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[30]
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an) Z Elektrochem Ang
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hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
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at
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37
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[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
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13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
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t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
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[72] Morley EW On the vapour-pressure of mercury at ordinary temperatures Phil Mag 7 662-661904
[73] Murgulescu IG Topor L Vapour pressure and molecular association of NaCl NaBr vapoursRev Roum Chim 11 1353-1360 1966
[74] Neumann K Voumllker E A torsion balance method for measurements of lowest vapor pressures(in German) Z Phys Chem 161 33-45 1932 Pedder JS Barratt S The determination of the vapour pressures of amalgams by a dynamicmethod J Chem Soc (London) 537-546 1933 Pfaundler L On the tension of mercury vapor in the interval 0degC to 10Phys Chem 63(3) 36-43 1897
[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
or ury melts (in German) Z f Elektrochemie 60 431-454 1956
(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
[96] Debenedetti Metastable Liquids Concepts and Principles Princeton NJ Princeton
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1321 1912 [98] Bender J On the critical temperature of mercury (in German) Phys Z 16 246-247 1915 [99] Birch F The electrical resistance and the critical point of mercury Phys Rev 41 641-648 1932 [100] Mathews JF The critical constants of inorganic substances Chem Rev 72(1) 71-100 1972 [101] Ambrose D Vapour-liquid critical properties Natl Phys Lab Div Chem Stand Teddington
UK p 60 1980 [102] Franck EU Hensel F Metallic conductance of supercritical mercury gas at high pressures Phys
Rev 147(1) 109-110 1966 [103] Kikoin IK Senchenkov AP Electrical conductivity and equation of state of mercury in the
temperature range 0-2000degC and pressure range of 200-5000 Atm Phys Metals Metallog 24(5) 74-89 1967
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[147] Zaitsau DH Verevkiapor pres d env
1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Table 6 Continued
First author No pts T range K
Estimated uncertainty
AAD RMS
Roeder [80] 7 413-614 2 100 111 Ruff [81] 12 478-630 gt20 2249 2578 Schmahl [82] 43 412-640 15 070 071 Schneider [83] 23 484-575 10 404 502 Scott [85] 1 293 2 111 na Stock [88] 3 253-283 20 1505 1680 Sugawara [9] 14 602-930 2 115 095 van der Plaats [89] 26 273-358 8665 2303 Villiers [90] 12 333-373 6 476 324 Volmer [91] 10 303-313 3 157 113 von Halban [92] 2 220-255 7 815 221 Young [93] 11 457-718 2 140 130
One outlier at 2886 K was not included in statistics na not applicable
22
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
5 Comparisons with Correlations from the Literature
Figures 5a and 5b compare correlations and tables for the vapor pressure of
mercury in different temperature regions obtained in the literature In these figures we
define percent deviation as 100(peq4-pcorr)peq4 where pcorr is the vapor pressure from
correlations in the literature and peq4 is that obtained from eq (4) We also show the
estimated uncertainty band of the new correlation eq (4) by a heavy black line The
existing correlations in the literature agree well with each other and with the new
correlation in the intermediate temperature region from about 400 K to the normal boiling
point In this region there is a fair number of high quality experimental data At low
temperatures the existing correlations differ from each other and some differ from the
new correlation As mentioned earlier there is a paucity of high quality direct vapor-
pressure measurements in this region and we feel that simultaneously using low
temperature heat capacity data allows our new correlation to display the proper behavior
in the low temperature region We also had access to newer data that some of the earlier
correlations did not include For example the Langersquos Handbook correlation [130] is
based upon the International Critical Tables of 1928 [131] while the most recent CRC
Handbook [132] values are based upon Vargaftik et al [8] which itself is based upon the
1972 book of Vukalovich and Fokin [4] Some earlier editions of the CRC Handbook (for
example the 57th Ed 1976-1977 p D-182) used the values from the International
Critical Tables of 1928 [131] Few correlations are applicable for higher temperatures
The maximum temperature limit of the Korea Thermophysical Properties Databank
correlation KDB [133] is given as 65415 K The maximum of the PTB equation [22] is
930 K these correlations should not be extrapolated outside of their given ranges At the
highest temperatures there are considerable differences among the various correlations
however there is also a lack of experimental measurements in this region The de Kruif
correlation [20 21] does not specifically state the temperature limits of the correlation
but the very thorough literature survey in the thesis [20] indicates that the only high
temperature data used in their work were those of Bernhardt [41] and Cailletet et al [45]
and they did not have access to the more recent measurements of Shpilrsquorain and
Nikanorov [86] Sugawara et al [9] or Schoumlnherr and Hensel [84] Langersquos Handbook
[130] includes a note in their table identifying 900 degC as the critical point this model
23
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
[26] Dalton J Experimental Essays II On the force of steam or vapour from water and various other liquids both in a vacuum and in air Mem Proc - Manchester Lit Philos Soc 5(2) 550-574
[27] g point of tin and the boiling point of mercury with a description of a
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[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
Oxford UK 1987
[34] mpfs bei verschiedenen Temperaturen
[35] (in German) Ann Phys Chem 17 193-200 1882
an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
[45] Colardeau E Riviegravere C Recherches sur les tensions de le vapeur de mercure
at
[47] he determination of high precision vapour pressure of mercury and its
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lumbia Vancouver Canada 1950
1801 Crichton J On the freezinself-registering thermometer Phil Mag (March) 147-148 1803 Beattie JA Blaisdell BE Kaminsky J An experimental study of the absolute tescale IV Reproducibility of the mercury boiling point The effect of pressure on the mercury boiling point Proc Am Acad Arts Sci 71 375-385 1937 Hall JA Barber CR The Internation1(4) 81-85 1950 Preston-Thomas H The international temperature scale of 1990 (ITS-90) Metrologia 27 3-10 1990
[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
[32] Preston-Thomas H The international practical temperature scale of 1968 amended edition of 1975 Metrologia 12 7-17 1976
[33] Regnault V Forces eacutelastiques des vapeurs Mem Acad Sci Inst Fr 26 506-525 1862 Avogadro A Ueber die Spannkraft des QuecksilberdaPogg Ann 27 60-80 1833 Hertz H On the pressure of saturated mercury
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[39] Smith A Menzies AWC Studies in vapor pressure IV A redetermination of the vapor pressures of mercury from 250deg to 435deg J Am C
[40] Menzies AWC The vapour pressures of liquid mercury Z Phys Chem 130 90-94 192[41] Bernhardt F Saturation pressure of mercury up to 2000 kgcm2 (in German) Phys Z 26(6) 265-
275 1925 [4 Bessel-Hagen E Ueber eine neue Form der Toumlplerschen Quecksilberluftpumpe und einige mit i
angestellte Versuche Ann Phys Chem 12(2) 425-445 1881 [4 Burlingame JW Dilute solutions of mercury in liquid binary alloys PhD Thesis University
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properties of solid liquid and ga809 1953 Cailletet L satureacutee Compt Rend 130 1585-1591 1900
[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
[49] Dauphinee TM The measurement of the vapour pressure of mercury in the intermediate pressure range PhD Thesis University of British Co
37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
[53] cadmium and mercury Phil Mag 33(193) 33-48
[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
[59] ohen Drucken Ber Bunsenges Phys Chem 70(910) 1154-1160 1966
13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
[65] 4
t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
[52] Durrans TH A treatise on distillation Perfumery and Essential Oil Record 11S 154-198 1920Egerton AC The vapour pressure of zinc1917 Ernsberger FM Pitman HW New absolute manometer for vapor pressures in theRev Sci Instrum 26(6) 584-589 1955 Galchenko IE Pelevin OV Sokolov AM Determination of the partial vapor pressvolatile component by the static method Industrial Laboratory 44(12) 1699-1700 1978 Galchenko IE Pelevin OV Sokolov AM Determination of the vapor pressure ofover melts in the Hg-Cd-Te system Inorganic Materials 20(7) 952-955 1984 Gebhardt A Uumlber den Dampfdruck von Quecksilber und Natrium Ber Dtsch Phys Ges 7 184-185 1905 HagenPhys Chem 16 610-618 1882 Hensel F Franck EU Elektrische Leitfaumlhigkeit und Dichte von uumlberkritischem gasfoumlrmigem Quecksilber unter h
[60] Heycock CT Lamplough FEE The boiling points of mercury cadmium zinc potassium and sodium Proc Chem Soc 28 3-4 19
[61] Hildenbrand DL Hall WF Ju F Potter ND Vapor pressures and vapor thermodynamic properties of some lithium and magnesium halides J C
[62] Hill CF Measurement of mercury vapor pressure by means of the Knudsen pressure gauge PhyRev 20 259-266 1922
[63] Hubbard SR Ross RG Slope anomaly in the vapour pressure curve of Hg Nature 295 6683 1982 Jenkins CHM The determodified manometric method Proc R Soc London A 110(754) 456-463 1926 Kahlbaum GWA Studies of vapor pressure measurements (in German) Z Phys Chem 13 14-55 189
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
deviates substantially from the other correlations at high temperatures The DIPPR [134]
and Yaws [135] correlations appear indistinguishable on the plot and both have adopted
a critical point of 1735 K and 1608 MPa Our correlation agrees very well with these
correlations up to about 1500 K where the differences are probably due to the critical
point adopted in the correlations Also the correlation of Schmutzler (as presented in
Goumltzlaff [13]) adopts a different critical point from the selection here it uses Tc = 1751 K
and pc = 1673 MPa We note that the tabulated values in the book by Hensel and Warren
[7] appear to have been generated from the Schmutzler [13] correlation
-10
-8
-6
-4
-2
0
2
4
6
8
200 250 300 350 400 450 500 550 600
Temperature K
100
[(p-p
eq(4
))p
eq(4
)]
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Triple point
Figure 5a Comparison of the new correlation eq (4) with previous compilations and
correlations in the low temperature region up to 600 K The uncertainty band for eq (4) is
indicated by a heavy black solid line
24
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
4
0(4)]
-10
-8
-6
-4
-2
600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800
Temperature K
100
[(p-p
eq(4
)
2
)peq
de Kruif
KDB
CRC
DIPPRYaws
Langes
Schmutzler
PTB
Normal boiling point
Critical point
Figure 5b Comparison of the new correlation eq (4) with previous compilations and
correlations in the high temperature region from 600 K to the critical temperature The
uncertainty band for eq (4) is indicated by a heavy black solid line
6 Detailed Comparisons for the Temperature Range 0 degC to 60 degC
The temperature range from 0 degC to 60 degC is of particular interest for this pro
Unfortunately in this region there are very few vapor pr
ject
essure data of high accuracy Our
e Figure
ta
approach as detailed above was to identify the data sets of highest quality and
supplement the vapor pressure data with low-temperature heat capacity data to improve
the behavior of the correlation at low temperatures and to ensure thermodynamic
consistency The data of Ernsberger and Pitman [54] are the only direct vapor pressure
measurements of low uncertainty (1 ) available in this region and were the only low-
temperature vapor pressure data used in the regression Figure 6a shows the deviations of
all data with estimated uncertainties of 3 or less in this temperature range whil
6b shows comparisons with all sets with estimated uncertainties of 6 or less The da
25
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
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[27] g point of tin and the boiling point of mercury with a description of a
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[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
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an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
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at
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[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
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[33] Regnault V Forces eacutelastiques des vapeurs Mem Acad Sci Inst Fr 26 506-525 1862 Avogadro A Ueber die Spannkraft des QuecksilberdaPogg Ann 27 60-80 1833 Hertz H On the pressure of saturated mercury
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[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
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37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
[53] cadmium and mercury Phil Mag 33(193) 33-48
[54] micron range
[55] ure of the
[56] mercury
[57]
[58] EB On the tensions of saturated mercury vapor at low temperatures (in German) Ann
[59] ohen Drucken Ber Bunsenges Phys Chem 70(910) 1154-1160 1966
13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
[65] 4
t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
[71]
7
[75]
[76] 0degC (in German) Ann
1925
calculation of certain thermodynamic properties of the saturated liquid and vapor Nat Bur Stand(US) J Res NBS 46(4) 334-348 1951
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[60] Heycock CT Lamplough FEE The boiling points of mercury cadmium zinc potassium and sodium Proc Chem Soc 28 3-4 19
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[62] Hill CF Measurement of mercury vapor pressure by means of the Knudsen pressure gauge PhyRev 20 259-266 1922
[63] Hubbard SR Ross RG Slope anomaly in the vapour pressure curve of Hg Nature 295 6683 1982 Jenkins CHM The determodified manometric method Proc R Soc London A 110(754) 456-463 1926 Kahlbaum GWA Studies of vapor pressure measurements (in German) Z Phys Chem 13 14-55 189
[66] Knudsen M Experimental determination of the pressure of saturated mercury vapors at 0degC and ahigher temperatures (in German) Ann Phys 29 179-193 1909 Knudsen M An absolute manometer (in German) Ann Phys 32(4) 89
[68] Kordes E Raaz F Aufnahme von Siedediagrammen binaumlrer hochsiedender Fluumlssigkeitsgemische Z Anorg Allg Chem 181 225-236 1929
[69] Mayer H On a new method for measurements of the lowest vapor pressures the vapor pressuresof mercury and potassium III Communicati1930 McLeod FRS On the pressuthe Meeting of the British Association for the Advancement of Science 443-444 1883 Millar RW The vapor pressures of potassium amalgams J Am Chem Soc 49 3003-3010 1927
[72] Morley EW On the vapour-pressure of mercury at ordinary temperatures Phil Mag 7 662-661904
[73] Murgulescu IG Topor L Vapour pressure and molecular association of NaCl NaBr vapoursRev Roum Chim 11 1353-1360 1966
[74] Neumann K Voumllker E A torsion balance method for measurements of lowest vapor pressures(in German) Z Phys Chem 161 33-45 1932 Pedder JS Barratt S The determination of the vapour pressures of amalgams by a dynamicmethod J Chem Soc (London) 537-546 1933 Pfaundler L On the tension of mercury vapor in the interval 0degC to 10Phys Chem 63(3) 36-43 1897
[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
or ury melts (in German) Z f Elektrochemie 60 431-454 1956
(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
[96] Debenedetti Metastable Liquids Concepts and Principles Princeton NJ Princeton
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Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
of both Busey and Giauque [44] and Douglas Ball and Ginnings [51] were not direct
measurements but rather were values obtained from their analysis of heat capacity dat
Our correlation does not agree with these sets to within their estimated uncertainties
neither do
a
the sets agree with each other to within these uncertainties The single data
point of Scott [85] at 293 K determined with a quartz fiber manometer with an estimated
timated
uncertainty and are represented well by the correlation
Figure 7 compares correlations in the literature with eq (4) for the temperature
range 273 K to 333 K (0 degC to 60 degC) There are four correlations that agree with eq (4)
to within our estimated uncertainty of 1 those by de Kruif [20 21] DIPPR [134]
Yaws [135] and Mukhachev et al [16] Yaws [135] does not state the uncertainty of his
equation however the DIPPR [134] equation reports an estimated uncertainty of less than
3 and the two correlations are almost indistinguishable from one another The DIPPR
correlation was developed by fitting vapor pressure data with a primary data set
consisting of 54 experimental points from Ambrose and Sprake [18] for temperatures
from 426 K to 771 K nine smoothed points from the correlation of Stull [11] for 399 K
to 596 K and 81 points from the tables in Vargaftik [136] for temperatures 273 K to
1073 K [137] The correlation of de Kruif [20 21] was developed by use of the method
uncertainty of 2 is represented by our correlation within this margin The
measurements of Volmer and Kirchoff [91] have a slightly higher (3 ) es
of Clark
26
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
-6
-2
0
2
4
6
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))eq
(4)]
-4
p
Douglas 1951Ernsberger 1955Busey 1953Volmer 1925Scott 1924
Figure 6a Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 3 or less
-20
-15
-10
-5
0
273 283 293 303 313 323 333Temperature K
100
[(p-p
eq(4
))
5peq
(4)
10
15
20
]
Douglas 1951Ernsberger1955Busey 1953Hildenbrand 1964Mayer 1930Volmer 1925Scott 1924Neumann 1932Knudsen 1909Knudsen 1910Poindexter 1925
Figure 6b Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with experimental data with estimated uncertainties of 6 or less
27
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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Rato3] KDB
2004 ea Thermo al erties Data (KDB) h w orgkdb Korea
ersity[13 ley J ng W Osc Row DIADE DIPP tion a
Eval nager 70 oun ity Prov UT 2[135] Yaws CL l Prop rties H Phys modyna ics En l
sport Health elate s for amp Inorg ic Che Grawssion 784 p
[13 aftik les on e The l Pro Liquids nd Ga ork ted Pr 2nd e
[13 ley R al com unic ber M ham Yo g Uni vo Ut2 20
[13 e E w DN Evalu ermo unctions rom eq onstans Far 2 539- 47 1
[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
24 [142] olmer M Estermann I On the evaporation coeff of solid a d liquid m (in
erman) Zeitschr f Physik 7 1-12 1921 [143] witt FB method of determ e llic vapou an
perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
-10
-8
-6
-4
-2
0
2
4
6
100
[(p-p
eq(
))p
eq(4
)]
273 283 293 303 313 323 333Temperature K
4
CRC 2004 edition
de Kruif 1971
Yaws 1999
KDB 2005
Langes ICT 1928
Goumltzlaff 1988
PTB 1995
DIPPR 2004
Mukhachev 1965
ASTM D6350
Figure 7 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with correlations from the literature
and Glew [138] that in addition to vapor pressure data used supplementary data such as
heat capacities Gibbs free energies of vaporization and enthalpies of vaporization to
develop the correlation The curve from the CRC Handbook 85th Edition is based on
that of Vargaftik et al [8] which itself is based upon Vukalovich and Fokin [4] The
Vukalovich and Fokin [4] source lists the data used in the development of the equation
and apparently they were unaware of the data of Ernsberger and Pitman [54] As
mentioned earlier Ernsberger and Pitman [54] give an estimated uncertainty of 1 for
s
al
oiling point of mercury The KDB correlation [133] is presented only as a set of
their measurements and they seem to be the most reliable vapor pressure measurement
in the 0 degC to 60 degC range The Mukhachev et al [16] correlation was developed from
caloric data such as heat of vaporization and heat capacities along with the norm
b
28
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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[1] 005
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[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
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[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
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37
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[54] micron range
[55] ure of the
[56] mercury
[57]
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13
hem Phys 40(10) 2882-2890 1964 s
82-
[64] mination of the vapour tensions of mercury cadmium and zinc by a
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t
[67] 0-842 1910
on (in German) Zeitschr f Physik 67 240-263
[70] re of the vapour of mercury at the ordinary temperature Report of
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7
[75]
[76] 0degC (in German) Ann
1925
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[73] Murgulescu IG Topor L Vapour pressure and molecular association of NaCl NaBr vapoursRev Roum Chim 11 1353-1360 1966
[74] Neumann K Voumllker E A torsion balance method for measurements of lowest vapor pressures(in German) Z Phys Chem 161 33-45 1932 Pedder JS Barratt S The determination of the vapour pressures of amalgams by a dynamicmethod J Chem Soc (London) 537-546 1933 Pfaundler L On the tension of mercury vapor in the interval 0degC to 10Phys Chem 63(3) 36-43 1897
[77] Poindexter FE Mercury vapor pressure at low temperatures Phys Rev 26 859-868
38
[78] Raabe G Sadus RJ Molecular simulation of the vapor-liquid coexistence of mercury J ChePhys 119(13) 6691-6697 2003
m
s 925
or ury melts (in German) Z f Elektrochemie 60 431-454 1956
(in German) Z
[82] ethod Three-term vapor pressure equation for mercury (in German)
[83] vapor pressure of tellurium (in German) Z Elektrochem Ang
[84] Hensel F Unusual thermodynamic and electrical properties of metallic solutions
[85] ur pressures of cesium and rubidium and a calculation of
[86] of mercury by the boiling
583
ow 3-54 786-790 1929
ture
[91] essures of solid and liquid benzophenone between 0deg und
[92] 5 1935
[94] 35(9) 1065-1067 1913
nsorship of the Internation Union of Pure and Applied Chemistry Commission on
[96] Debenedetti Metastable Liquids Concepts and Principles Princeton NJ Princeton
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Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
coefficients with a range of applicability and we do not know the data used in its
development it is consistently lower than our correlation The PTB curve [22] with a
reported maximum uncertainty of 4 is very different in shape from all the others
investigated This analysis did not incorporate caloric data and the experimental data in
the 0 degC to 60 degC range that were used in the regression were those of Poindexter [77]
and Neumann and Voumllker [74] The equation recommended in the ASTM Standard
D6350 [139] is presented in terms of a concentration in nanograms per milliliter We
converted the expression to vapor pressure by applying the ideal gas law and using
relative molar mass [129] of 20059 and gas constant [121] R = 8314472 J(molK) It
agrees well with the values from Langersquos Handbook [130] The curve from Langersquos
Handbook [130] deviates the most from our correlation approaching 10 at 273 K and
gives vapor pressures that are lower than all the other correlations The curve in Langersquos
Handbook [130] is based upon the 1928 International Critical Tables (ICT) [131] and w
developed with only the limited data and computational methods available at that time
Since it has been used extensively in handbooks and in industrial standards
further discussion of the 1928 International Critical Tables is warranted A total of 28
references are given for the 1928 International Critical Tables with the most recent date
1926 In addition some of these references are not original data but rather analysis of
literature data [17 140-143] and only 8 of the references [53 66 67 72 76 77 85 90]
contain data in the range 273 K to 333 K Details are not given concerning how the data
were weighted or the uncertainties of the numbers presented and it is difficult to know
the exact procedure used to obtain the values in the table However it was not
uncommon prior to the widespread use of computers to employ graphical methods For
example Stull [11] in 1947 states ldquothe analytical meth
a
as
d
odwas based on semilogarithmic
es
charts measuring 30 times 42 inches (where 1 mm = 1deg C) and colored map tacks
representing the plotted points over which a taut thread was stretchedrdquo Comparisons
with the data cited in the International Critical Tables (Figure 8) indicate that the valu
of the 1928 International Critical Tables (ICT) [131] in the range 0 degC to 60 degC are in
closest agreement with the 1909 data of Knudsen [66] Figure 8 shows the percent
deviations from eq (4) for all of the data cited in the 1928 ICT the ICT values [131] and
the data of Ernsberger and Pitman [54] The 1955 data of Ernsberger and Pitman [54]
29
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
Physical Chemistry Science and Engineering ed Prausnitz
[8] and
[9] n the equation of state of mercury vapour Bulletin of
[10]
[11] e of pure substances Inorganic compounds Ind Eng Chem 39(4) 540-
[12] Powers MD The vapor pressure of liquid mercury from the triple point to the
[13] fluiden
[14] RW Gilmour JC The vapor pressures of monatomic vapors Rev Mod Phys 13
[15] quid elements RCA Review
e thermodynamic
[18] 0
n 383
[20] if CG The determination of enthalpies of sublimation by means of thermal conductivity
[21] if CG van Ginkel CHD Langenberg A Vapour pressure and thermodynamic function
[23] m (in Japanese) Trans JSME 17(62) 70-77
[24] pressure equations for the metallic elements
[25] e of the Elements (translated from the Russian by JI Carasso)
[2] Holman GJF ten Seldam CA A critical evaluation of the thermophysical properties of mercury J Phys Chem Ref Data 23(5) 807-827 1994 BettinS16-S23 2004 Vukalovich MP Fokin LR Thermophy1972 Gmelin Handbuch der Anorganischen Chemie Quecksilber No 34 Verlag Chemie WeinheimBergstrasse 1960 Sakonidou EP Assael MJ Nieto de Castro C Van den Berg HR Wakehareview of the experimental data for the thermal properties of liquid mercury gallium and indium in Thermal C
[7] Hensel F Warren WW Jr Fluid Metals The Liquid-Vapor Transition of Metals Princeton Princeton University Press 1999JM Brewer L 244 p Vargaftik NB Vinogradov YK Yargin VS Handbook of Physical Properties of Liquids Gases New York Begell House 1996 3rd ed 1359 p Sugawara S Sato T Minamiyama T OJSME 5(20) 711-718 1962 Hicks WT Evaluation of vapor-pressure data for mercury lithium sodium and potassium JChem Phys 38(8) 1873-1880 1963 Stull DR Vapor pressur550 1947 Epstein LFcritical point Atomic Energy Commision AECU-1640 1951 Goumltzlaff W Zustandsgleichung und elektrischer Transport am kritischen Punkt desQuecksilbers Dr rer nat Thesis Philipps-Universitaumlt Marburg Marburg Germany 1988 Ditchburn310-327 1941 Honig RE Kramer DA Vapor pressure data for the solid and li30(2) 285-288 1969
[16] Mukhachev GA Borodin VA Poskonon YA Temperature variation of thproperties of mercury Russ J Phys Chem 39(8) 1080-1083 1965
[17] Laby TH A recalculation of the vapor pressure of mercury Phil Mag 6(16) 789-796 1908 Ambrose D Sprake CHS The vapour pressure of mercury J Chem Thermodyn 4 603-621972
[19] Kelley KK Contributions to the data on theoretical metallurgy III The free energies of vaporization and vapor pressures of inorganic substances US Bureau of Mines BulletiWashington DC 1935 de Krumanometers PhD Thesis Rijksuniversitlit Utrecht Utrecht The Netherlands 1971 de Kruchanges of mercury Recl Trav Chim Pays-Bas 92 599-600 1973
[22] PTB Physikalisch-Technische Bundesanstalt (PTB)-Stoffdatenblaumltter SDB 12 Mercury PTB Braunschweig and Berlin 1995 Uchida H Mercury vapour tables and i-s diagra1951 Alcock CB Itkin VP Horrigan MK Vapour 298-2500 K Can Metall Q 23(3) 309-313 1984 Nesmeyanov AN Vapor PressurNew York Academic Press 1963 469 p
36
[26] Dalton J Experimental Essays II On the force of steam or vapour from water and various other liquids both in a vacuum and in air Mem Proc - Manchester Lit Philos Soc 5(2) 550-574
[27] g point of tin and the boiling point of mercury with a description of a
[28] mperature
[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
Oxford UK 1987
[34] mpfs bei verschiedenen Temperaturen
[35] (in German) Ann Phys Chem 17 193-200 1882
an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
[45] Colardeau E Riviegravere C Recherches sur les tensions de le vapeur de mercure
at
[47] he determination of high precision vapour pressure of mercury and its
tional Conference on Calorimetry and Thermodynamics Warsaw
[48] cells J Chem Phys 38(11) 2725-2735 1963
lumbia Vancouver Canada 1950
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
were not available to the authors of the ICT Table however it is the primary data
we used in the low temperature region In addition Ernsberger and Pitman [54] noted
that although the ICT tables are given to four significant figures the uncertainty
probably 5 to 10 due to the uncertainties in the measurements upon which the ICT
table for mercury is based Further discussion on the Knudsen [66] data follows
appears that the ICT tables agree most closely with this particular data set
source
is
since it
-20
-10
0
10
20
30
40
50
60
270 280 290 300 310 320 330Temperature K
100
[(p-p
eq(4
))eq
(4)]
p
ICT 1928Egerton 1917Haber 1914Hill 1922Knudsen 1910Knudsen 1909Morley 1904Pfaundler 1897Poindexter 1925Scott 1924Villiers 1913Ernsberger 1955
Figure 8 Comparison of the new correlation eq (4) in the temperature range 273 K to
333 K with data cited in the references for the 1928 International Critical Tables (ICT)
[131] the values in the 1928 ICT and the data of Ernsberger and Pitman [54]
The vapor pressure data of Knudsen [66] were obtained in 1909 using an effusion
method In fact it was the very first measurement of this type and the method is now
often called ldquothe Knudsen effusion methodrdquo or ldquothe Knudsen methodrdquo Several variants
of this method have been developed and have been in continuous use from 1909 until the
present day Cater [144] discussed the state of the art in of the effusion method in 1978
as recently as 2006 Zaitsau et al [145] used the Knudsen method to measure the vapor
30
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
pressure of ε-caprolactam The basic method developed by Knudsen involves the flow
e or tube With a known orifice size
and geometry one can measure the flow rate and calculate the vapor pressure with
equations based on kinetic theory The measurements that Knudsen made in 1909 were
done very carefully One measurement at 0 degC took 13 days to completemdashhis method of
detection was to condense the effusing mercury vapor and measure its volume at room
temperature in a capillary tube located below the condenser However even today with
state of the art equipment estimated uncertainties for mass-loss Knudsen effusion
methods are about 5 [146 147] for pressures on the order of 10-1 Pa to 1 Pa EPA
guidelines [148] give an estimated repeatability of 10 to 30 for mass-loss effusion
methods for the pressure range 10-3 Pa to 1 Pa Measurements at such low pressures are
difficult some factors that can contribute to the uncertainty are temperature measurement
and control determination of the weight-loss and knowledge of the orifice geometry For
finite orifice lengths the geometry must be well known in order to compute the Clausing
re is a 1 uncertainty associated with the direct
manometric method of Ernsberger and Pittman [54]
One can also demonstrate that the ICT Tables apparently based on the data of
Knudsen [66] are thermodynamically inconsistent with low temperature heat capacity
data Figure 9a shows comparisons of the calculated and experimental values of heat
capacity and Figure 9b compares the experimental and calculated values for the vapor
pressure using the present vapor pressure equation eq (4) Sakonidou et al [6] reviewed
the availability of heat capacity data for mercury and identified three major sets of heat
capacity data for the low temperature (below 60 degC) region Busey and Giauque [44] (01
uncertainty) Douglas et al [51] (1 uncertainty) and Amitin et al [123](1
uncertainty) These sets of heat capacity data are represented to within their experimental
uncertainties as are the vapor pressure data of Ernberger and Pitman [54] (1
uncertainty) The Knudsen data [66] are represented to within 5 to 10 a level
consistent with the effusion technique with the highest deviations at the lowest
temperatures Therefore our equation represents all of these data sets to within their
of vapor from a space where it is in equilibrium with a solid or a liquid at a known
temperature into a high vacuum through a fine hol
factor which corrects for the fact that some molecules may strike the orifice wall and be
returned to the cell [144] In contrast the
31
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
uncertainties and the heat capacity data are thermodynamically consistent with the vapor
pressure data However if one refits the vapor pressure equation but instead of using the
n
o longer possible to represent the heat capacities to
within their experimental uncertainty as shown in Figure 10a This indicates that the
Knudsen data at a 2 uncertainty level are thermodynamically inconsistent with the
heat capacity measurements Therefore the 1928 ICT Tables that represent the Knudsen
data to better than 2 are thermodynamically inconsistent with the heat capacity
measurements of Busey and Giauque [44] Douglas et al [51] and Amitin et al [123] To
summarize the effusion data of Knudsen [66] can be assigned a temperature-dependent
uncertainty of 5 to 10 any attempt to ascribe a smaller uncertainty to this data set
would be inconsistent with the more recent data of Ernsberger and Pitman [54] Busey
and Giauque [44] Douglas et al [51] and Amitin et al [123]
data of Ernsberger and Pitman [54] as primary data one instead uses the data of Knudse
[66] and adjusts the weights so that the resulting vapor pressure equation represents the
Knudsen data to within 2 it is n
32
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
20
-20
-15
-10
-05
00
05
10
1510
0(Cp
exp-C
pcal
) Cp
exp
230 240 250 260 270 280 290 300 310Temperature K
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
Figure 9a Comparison of heat capacities calculated with the present correlation eq (4)
ental heat capacity data and eq (2) with experim
-10
-8
-6
-4
-2
0
270 280 290 300 310 320 330Temperature K
100
( pex
p-p
cal)p
exp
2Ernsberger and Pitman (1955)Knudsen (1909)
Figure 9b Comparison of vapor pressures calculated with the present correlation eq (4)
with experimental vapor pressure data
33
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
-4
-3
-2
-1
0
1
2
3
230
Busey and Giauque (1953)Amitin et al (1979)Douglas et al (1951)
pp
caex
l)Cp
exp-Cp
100(C
240 250 260 270 280 290 300 310Temperature K
Figure 10a Comparison of heat capacities calculated with eq (1) and eq (2) subject to
the constraint that the vapor pressure data of Knudsen be represented to within 2 with
experimental heat capacity data
-2
0
2
4
6
8
10Knudsen (1909)Ernsberger and Pitman (1955)
pex
p)
- pca
l( p
exp
100
270 280 290 300 310 320 330Temperature K
10b ComFigure parison of vapor pressures calculated with eq (1) and eq (2) subject to
on th the c straint that the vapor pressure data of Knudsen be represented to within 2 wi
experimental vapor pressure data
34
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
7 Conclusions
We de veloped a new correlation for the vapor pressure of mercury that is valid
the triple point [30] 2343156 K to the critical point [105] 1764 K using a
of the uncertainties of these data as discussed above The estimated uncertainty at a
coverage factor of two varies from 3 near the triple point to 1 for temperatures from
273 K ture region from 400 K to the
al boiling point at 62977 K for tem
int
sti
s
are 26-
de
this pro
REP
T
Guest R
Harvey
from
Wagner-type equation We have determined the uncertainties to be associated with the
equation through our comparisons with the primary experimental data and consideration
to 400 K 015 for the intermediate tempera
norm peratures above the normal boiling point but
below about 900 K it is 05 and for temperatures between 900 K and the critical po
mate the uncertainty is abwe e out 5 The new correlation gives a normal boiling
point (101325 kPa) of 62977 K
This project was supported in part by the Western Research Institute and wa
d with the support of the US Department of Energy under Award Nprep o DE-FC
98FT40323 However any opinions findings conclusions or recommendations
expressed herein are those of NIST and do not necessarily reflect the views of the DOE
We thank the staff of the Department of Commerce Boulder Laboratories Library for
their dication and cheerful assistance in obtaining the historic literature necessary for
ject and Dr Harro Bauer (Physikalisch-Technische Bundesanstalt
Braunschweig Germany) for providing us with a copy of ref [22] We thank NIST P
student Justin Chichester for assistance with the preparation of this manuscript and NIS
esearcher Ilmudtin Abdulagatov for assistance with Russian literature We also
acknowledge helpful discussions with our NIST colleagues Mark McLinden Allan
and Gerald Mitchell and with Dr John Schabron of the Western Research
Institute
35
9 References
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
9 References
Selin NE Mercury is rising Is global action needed to protect human health and the environment Environment 47(1) 22-35 2
[1] 005
[3] H Fehlauer H Density of mercurymdashmeasurements and reference values Metrologia 41
[4] sical Properties of Mercury Moscow Standards Press
[5]
[6] m WA A
onductivity 24 Thermal Expansion 12 Joint Conferences Pittsburgh PA 1999
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
[26] Dalton J Experimental Essays II On the force of steam or vapour from water and various other liquids both in a vacuum and in air Mem Proc - Manchester Lit Philos Soc 5(2) 550-574
[27] g point of tin and the boiling point of mercury with a description of a
[28] mperature
[29] al Temperature Scalemdash1948 Revision Br J Appl Phys
[30]
Oxford UK 1987
[34] mpfs bei verschiedenen Temperaturen
[35] (in German) Ann Phys Chem 17 193-200 1882
an) Z Elektrochem Ang
[38] R Vapor pressure and Antoine
all KR Editor Landolt-Boumlrnstein
hem Soc 32 1434-1447 1910 7
2] hr
3] of ia PA 1968
mic s Heat of fusion and vaporization J Am Chem Soc 75 806-
[45] Colardeau E Riviegravere C Recherches sur les tensions de le vapeur de mercure
at
[47] he determination of high precision vapour pressure of mercury and its
tional Conference on Calorimetry and Thermodynamics Warsaw
[48] cells J Chem Phys 38(11) 2725-2735 1963
lumbia Vancouver Canada 1950
1801 Crichton J On the freezinself-registering thermometer Phil Mag (March) 147-148 1803 Beattie JA Blaisdell BE Kaminsky J An experimental study of the absolute tescale IV Reproducibility of the mercury boiling point The effect of pressure on the mercury boiling point Proc Am Acad Arts Sci 71 375-385 1937 Hall JA Barber CR The Internation1(4) 81-85 1950 Preston-Thomas H The international temperature scale of 1990 (ITS-90) Metrologia 27 3-10 1990
[31] Marsh KN ed Recommended Reference Materials for the Realization of Physicochemical Properties Blackwell Scientific
[32] Preston-Thomas H The international practical temperature scale of 1968 amended edition of 1975 Metrologia 12 7-17 1976
[33] Regnault V Forces eacutelastiques des vapeurs Mem Acad Sci Inst Fr 26 506-525 1862 Avogadro A Ueber die Spannkraft des QuecksilberdaPogg Ann 27 60-80 1833 Hertz H On the pressure of saturated mercury
[36] Ramsay W Young S On the vapour-pressures of mercury J Chem Soc (London) 49 37-50 1886
[37] Haber F Kerschbaum F Measurement of low pressures with a vibrating quartz filament Determination of the vapor pressure of mercury and iodine (in GermPhys Chem 20 296-305 1914 Dykyj J Svoboda J Wilhoit RC Frenkel M Hall Kconstants for hydrocarbons and sulfur selenium tellurium and halogen containing organic compounds in Vapor Pressure of Chemicals subvolume A HNumerical Data and Functional Relationships in Science and Technology Group IV Physical Chemistry Volume 20 Springer 1999
[39] Smith A Menzies AWC Studies in vapor pressure IV A redetermination of the vapor pressures of mercury from 250deg to 435deg J Am C
[40] Menzies AWC The vapour pressures of liquid mercury Z Phys Chem 130 90-94 192[41] Bernhardt F Saturation pressure of mercury up to 2000 kgcm2 (in German) Phys Z 26(6) 265-
275 1925 [4 Bessel-Hagen E Ueber eine neue Form der Toumlplerschen Quecksilberluftpumpe und einige mit i
angestellte Versuche Ann Phys Chem 12(2) 425-445 1881 [4 Burlingame JW Dilute solutions of mercury in liquid binary alloys PhD Thesis University
Pennsylvania Philadelph[44] Busey RH Giauque WF The heat capacity of mercury from 15 to 330degK Thermodyna
properties of solid liquid and ga809 1953 Cailletet L satureacutee Compt Rend 130 1585-1591 1900
[46] Callendar HL Griffiths EH On the determination of the boiling-point of sulphur and on a method of standardising platinum resistance thermometers by reference to it Experiments madethe Cavendish Laboratory Cambridge Phil Trans R Soc Lond A 182 119-157 1891 Cammenga HK Timportance as reference pressure for studies on vapour pressure and rate of evaporation in Proceedings of the 1st InternaPoland 1969 Carlson KD Gilles PW Thorn RJ Molecular and hydrodynamical effusion of mercury vaporfrom Knudsen
[49] Dauphinee TM The measurement of the vapour pressure of mercury in the intermediate pressure range PhD Thesis University of British Co
37
[50] Dauphinee TM The vapor pressure of mercury from 40degC to 240degC (5 microns to 6 cm) Measured by the streaming method J Chem Phys 19 389-390 1951
[51] Douglas TB Ball AF Ginnings DC Heat capacity of liquid mercury between 0deg and 450degC
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41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
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19] Kin B Al-N A for corre and ext ap sure data t wer tembel
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Dis e Regress TI Natl Inst nd Techn 29] Los
0] Lange NA ed Handbook of ChemD Atomi ts ements P
istry 10th ed McGraw-Hill New York 1967 ppl Che
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40
[131] Washburn EW ed International Critical Tables of Numerical Data Physics Chemistry and chnology e III McGraw-Hill New York 1928
[13 DR Handb ok of and Physics 85th Edition ed CRC Press Boca n FL
[13 Kor physic Prop bank ttpww cheric
Te Volum2] Lide ed CRC o Chemistry
Rato3] KDB
2004 ea Thermo al erties Data (KDB) h w orgkdb Korea
ersity[13 ley J ng W Osc Row DIADE DIPP tion a
Eval nager 70 oun ity Prov UT 2[135] Yaws CL l Prop rties H Phys modyna ics En l
sport Health elate s for amp Inorg ic Che Grawssion 784 p
[13 aftik les on e The l Pro Liquids nd Ga ork ted Pr 2nd e
[13 ley R al com unic ber M ham Yo g Uni vo Ut2 20
[13 e E w DN Evalu ermo unctions rom eq onstans Far 2 539- 47 1
[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
24 [142] olmer M Estermann I On the evaporation coeff of solid a d liquid m (in
erman) Zeitschr f Physik 7 1-12 1921 [143] witt FB method of determ e llic vapou an
perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
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19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
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Růžič ů K Vapor pressure of diethyl phthalate Therm
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1sures an3
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] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
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perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
[131] Washburn EW ed International Critical Tables of Numerical Data Physics Chemistry and chnology e III McGraw-Hill New York 1928
[13 DR Handb ok of and Physics 85th Edition ed CRC Press Boca n FL
[13 Kor physic Prop bank ttpww cheric
Te Volum2] Lide ed CRC o Chemistry
Rato3] KDB
2004 ea Thermo al erties Data (KDB) h w orgkdb Korea
ersity[13 ley J ng W Osc Row DIADE DIPP tion a
Eval nager 70 oun ity Prov UT 2[135] Yaws CL l Prop rties H Phys modyna ics En l
sport Health elate s for amp Inorg ic Che Grawssion 784 p
[13 aftik les on e The l Pro Liquids nd Ga ork ted Pr 2nd e
[13 ley R al com unic ber M ham Yo g Uni vo Ut2 20
[13 e E w DN Evalu ermo unctions rom eq onstans Far 2 539- 47 1
[13 ard T d for Mercur and Analysis in Natural Gas by Atomic Fluorescence trosco 50-98 STM al R 2003
40] Egerton AC Note on the determination of chemical constants Phil Mag 39 1-20 1920 on vapour pressures of monatomic substances Phil Mag 48 1048-1054
24 [142] olmer M Estermann I On the evaporation coeff of solid a d liquid m (in
erman) Zeitschr f Physik 7 1-12 1921 [143] witt FB method of determ e llic vapou an
perimental application to the cases of sodium and y Phil Mag 4 546-554 1902 [144] ter ED usion m ate of the art in Proceedings o 0th Mat
search S m on C aracteriz f High T ture Vap rs and Ga at Bur S) Spec lication 61 1979
[145] itsau DH lechka Y U Kabo GJ Kolpikau AN Emely enko V intz Aerevkin S rmodynamics of t imation and of the vaporization of ε-caprolactam J em Eng 51 130- 5 2006
[146] Rohhaacuteč V ka K R žička V Zaitsau DH Kabo GJ Diky V Aim J Chem odyn 36 929-937 2004
n SP Paulechka YU Kabo GJ Sevruk VM Comprehensive study of thal es of vaporization of cyclohexyl esters Eng Data 48 1393
400 200[148 S 8307950 V por Pressur EPA Repo 712-C-96-043
ubstances (OPPTS) US Environmental Protection Agency 1996
Univ 2005
4] Row R Wildi V arson JL ley RL M R Informa nd Data uation Ma v2 Brigham Y g Univers o 004
Chemica e andbook ical Ther m vironmentaTran Safety amp R d Propertie Organic an micals Mc -Hill Profe al 1999
6] Varg NB Tab th rmophysica perties of a ses New YHals ess 1975 d
7] Row8460
L person06
m ation to Hu L Brig un versity Pro ah
8] Clark CW Gle ation of th dynamic f f ulibrium c ts Tran ad Soc 6 5 966
9] Stand est Metho y SamplingSpec py D-63 A Internation eapproved
[1[141] Egerton AC Note
19V icients n ercuryGJeex
A new ining the vapour-density of m ta rs and mercur
Ca The eff ethod at 69 current st f the 1 erials Re ymposiu h ation o empera o ses N Stan (U ial Pub 5 Za Pau an N He V P The he sublCh Data 13
Růžič ů K Vapor pressure of diethyl phthalate Therm
[147] Zaitsau DH Verevkiapor pres d env
1sures an3
pi J Chem -
] Product Properties Test Guidelines OPPT a e rt Office of Prevention Pesticides and Toxic S
41
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Appendix A Detailed Listing of Experimental Data for the Vapor Pressure of ercur
Al eratures have been converted to ITS-90 Data are arranged alphabetically by first
auDa brose and Sprake [18]
T p kP T K p kP
M y
l temp
thor ta from Am
T K p kPa K a a 379934 681168 23790046 92 635136 111503 400340 685426 2539 636491 114202
702724 3278 621615 87311 711623 3719 623249 89986 726554 4566 92662 739690 5430 95342 749788 6178 98055 771124 8025 100770
451381 1101 481650 3023 630924 103440 488128 3689 632343 106101
4 494925 4522 633750 108792 500619 5339 635136 111504 506657 6342 636492 114202 513690 7708 621622 87323 520258 9205 623266 90010 526171 10753 624853 92671 533782 13074 626418 95353 541589 15879 627958 98060 546934 18080 629466 100764 555219 21998 630924 103441 562504 26013 632343 106101 572032 32173 633750 108794
2 579202 37584 635130 111489 3 587994 45215 636492 114202
71 53760 621625 87331 623267 90014
597320 54686 612930 74144 624855 92672 605650 64484 621863 87728 626413 95348 611991 72866 628996 99929 627951 98043 6 7 629758 101311 629465 100764 6 8 630156 102037 630923 103440 628883 99711 621619 87316 632342 106098 629949 101643 623258 90004 633747 108789
624850 92667 635135 111501 6 100600 626421 95363 636488 114195
121141 627960 98061 133558 629464 100768
654707 155987 630923 103440 663194 179295 632340 106099 671779 205659 633748 108792
0139 33 417095 0293 08 426204 0424 75 432281 0538 09 624850 439292 0706 39 626410 441719 0774 83 627956 447681 0964 26 629467
454121 1213 56320 1309
462634 1627 469182 2024 474565 2414 479040 2784 485150 3369 491856 4128 497530 4882 533454 12965 541345 15780 549473 19193
2
554721 1742 562759 572231
6162 2313
579977 38203 5964589082 46244 605005 63675
2114 86564 2780 97795
638367 118032 29365
639863 645494
42
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Beattie Blaisdell and Kaminsky [28] T K p kP T K p kPa T K p kPa a
6297632 101325 6356476 112 6311879 103940 492 6297648 101325 6354589 112121 6326278 106646
6341509 109565 6339426 109160 6328014 106976 6349149 111047 6314044 104344 6336486 108587
6297663 101325 6299633 101688 6322578 105943 6284226 988973 6306593 102963
6245575 921883 6268527 961257 6291704 100244 4 6253936 93 6276159 974703 6232927 90 6260489 947299 6230797 89 6245171 921186 6249884 92 6229920 895730 6267624 959670 6282268 985483 6297562 101
Data from Bern
p kPa T p T K p kPa
6297666 101325 6297676 101325 6297632 101325
6229608 895232
6260545 94739 6046 6276855 975908 0733 6290765 100075 7188 6305802 102819 9141 6320069 105472 6334298 108168 6347126 110655 312
T K
hardt [41] K kPa
693 3432 1074 9807 1619 125500 693 3138 1114 12750 1663 146100
1174 14910 1674 155900 1199 16670 1685 164400 1368 46090 1685 173600 1488 88260 1685 181400 1553 104000 1706 198100 1608 105400 1614 111800 1619 118700
Dat ess ]
743 5688 753 5198 794 9807 794 1079 844 1618 854 1471 944 3334
1004 6865
a from B el-Hagen [42T K p kPa 273 000197 293 000268
43
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Burlingame [43]
Dat usey que [44]
Data
a from B and Giau
Data from Cailletet Colardeau and Rivigraveere [45]
from Callendar and Griffiths [46] TK p kPa
62979 101325 62995 101325
T T K p kPa K p kPa T K p kPa 3772 456010-2 4736 2318 4089 204510-1
3771 461310-2 4736 2321 3436 718610-3
3436 699910-3
3437 714610-3
3436 714610-3
3437 703910-3
3437 709310-3
4736 2314 4736 2353
-1 4736 2333 4736 2337
1 2 2
T p kPa
4432 812610-1
3771 454610-2 4432 806910-1
3770 461310-2 4432 808310-1
3770 456010-2 4432 816210-1
3771 450610-2 4432 819410-1
3772 442610-2 4735 2297 3771 461310-2 4735 2306 4089 207410-1
4089 207010-1
4088 2122104088 213410-1
44088
089 97110-1 4736 2341 4736 203810-1 316
4089 204210-1 4736 322
T K p kPa K 23432 30710-7 50001 5256 2 2 52502 1044101
55003 1947101
57503 3429101
-4 60004 5757101
3 2 62504 9274101
62992 1013102
65003 1437102
67503 2156102
70002 3140102
72501 4452102
75000 6165102
p T K p kPa
5002 2410-6
27500 29815 267
3311010
-5
-4
29998 311102498 0510-3
-234997 10310-237497 414410
39998 139710-1
42499 407710-1
44999 1054 47500 2458
T K p kPa T K kPa 673 213102 924 3 1154 16410445103
723 431102 974 5 7
1 3 10 103 874 226103 1124 1393104
07103
774 811102 1024 30103
824 4010 74 104
44
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Carlson Gilles and Thorn [48] T K p kPa T K p kPa
3 3 -4 4 2 -10138 506410 0628 7181032408 194710-3 44829 1652 33697 462610-3 49921 8371 34827 930610-3 54883 3145101
37217 422610-2 Dat auph 50] a from D inee [49
T K p kPa T K p kPa 45488 12407 34508 7 -3447391044455 8 1 -2
6 361 31 20031710-2
39641 1198410-1 40529 1788510-1
-1 48327 32547 4 2 -1 5
36 0-1 -3
58 0-1 -4
17 --4
Dat ougl nd Ginnin s [51]
T K p kPa
635310-1 35345 264961038291 096810-2
40517 16799101390 579410 1353 77820
42197 6501 33282 346241043336 1421 31402 9217910
32372 8119103 30500 4170310
a from D as Ball a gT K p kPa T K p kPa
23430 292110-7 41313 2466310-1 61319102 74557101
25317 3 62977102 10133102
2 63318102 10772102
1 47 15 23029 65318102 152074102
29814 258010-4 49316 42859 67318102 210201102
31313 845310-4 51317 75902 69317102 285011102
53317 12863101 71317102 379714102
3 1 -2 5 2 1 7331 4973 3 753 6431 5 773 819
Dat gerto
T p
11410-6 43314 5572210-1
27315 66110-5 45315 11697 29314 69110-4 3
33312 3472810-3
5312 212610 5318 096310 6102 80102
37312 694410-2 57318 2986101 15102 00102
39313 002810-1 59319 0299101 15102 32102
a from E n [53] T K p kPa T K p kPa K kPa
30683 532010-4 29804 242610-4 30 557853 310-4
30693 502610-4 29586 20 -4 29 16820 -4 30 50655 -4 30 55455 -4 30 55455 -4 30 55416 -4 30 55420 -4 30 55720 -4 5
2310 414 010-4
30743 522610-4 29586 2310 723 610-4
30718 514610-4 30823 4610 833 610-4
28864 861310-5 30853 7310 833 610-4
30733 488010-4 30853 7310 833 610-4
27315 252010-5 29414 8010 833 610-4
30173 337310-4 29586 1310 853 310-4
29804 238610-4 29586 131030173 329310-4 30823 54610-4
45
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Ernsberger and Pitman [54] T K p kPa T K p kPa
28522 845310-5 31515 994910-4
28815 111310-4 31817 124210-3
29110 144810-4 32115 153910-3
29411 185210-4 324 12 190 10-3
29722 241210-4 32663 226010-3
-4 29324 173510-4
3 3 2 2
Dat ebh
T K p kPa T K p kPa
0
30025 3116100318 93410-4 9622 22610-4
30617 500510-4 29920 286510-4
30923 635810-4 31211 792910-4
a from G ardt [57]
40313 14710-1 45315 123 4 2 46315 173
47315 236 48316 320
44314 84010-1 Data from Haber and Kerschbaum [37]
T K p kPa
1313 4010-1
42313 37310-1
43314 57310-1
293142 168010-4
Data from Hagen [58]
T K p kPa 27315 20010-3
32313 56010-3
37312 28010-2
42313 25610-1
47315 2126 Data from Hertz [35]
T K p kPa T K p kPa 36252 21310-2 45785 1472 39013 94710-2 46355 1719 42734 46510-1 47615 2713 43894 73610-1 48006 3010 45054 109
Data from Heycock and Lamplough [60]
T K p kPa 62889 101325
Data from Hildenbrand Hall Ju and Potter [61]
T K p kPa T K p kPa 2954 20810-4 2950 21010-4
2968 22610-4 2998 30510-4
2970 23310-4 3316 30110-3
46
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data ill [62]
p from HT K kPa T K p kPa
27245 4 4010-5 29714 34910-4
27885 7 1 1 1 1 2 3 2 3
Data nkins [
p
3310-5 29814 36410-4
28454 2310-4 29873 38910-4
28474 1510-4 29993 41910-4
28474 0910-4 30173 49310-4
28614 2910-4 30303 54310-4
29344 4910-4 30393 56710-4
29594 0710-4 30743 71710-4
29614 9910-4 30803 76710-4
29614 1310-4
from Je 64] T K kPa T K p kPa
47916 227 60019 556101
49366 380
1 1 1
2 13 13 14
ata from Kahlbaum [65] T K p kPa T K p kPa
60419 607101
51117 647 61519 776101
52067 827 62319 885101
52617 01101 63119 103102
53267 21101 63771 116102
54968 85101 64374 127102
56168 513101 65377 508102
57668 56101 66431 789102
58168 79101 67083 987102
58969 47101
DT K p kPa
3 11 42734 46410-1 45905 1527 9253 610-1
39783 1 43224 56410-1 46425 1797 39903 16810 43424 58510-1 46625 1867 40423 28110-1 43574 61710-1 46985 2212 40723 22110-1 43824 68310-1 47255 2332 40813 24310-1 44184 80310-1 47495 2549 41173 29310-1 44624 101 47795 2805 41333 35310-1 44834 104 47906 2864 41483 31310-1 44944 105 48206 3097 41743 26710-1 44994 109 48376 3357 41833 38110-1 45004 105 48746 3836 42023 36910-1 45275 117 48976 4117 42133 39610-1 45405 126 49296 4573 42213 42510-1 45475 125 42464 43710-1 45615 1409
8310-1
-1
47
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Knudsen [67] T K p kPa T K p kPa
26316 1 1010-5 28884 11410-4
27315 2 55 8
Dat nudse
9010-5 29374 16710-4
28005 010-5 29754 22610-4
28424 2010-5
a from K n [66] T K p kPa T K p kPa
27315 2 46110-5 30863 571310-4
28025 4 1 1 3
Dat ordes 8]
90210-5 31293 795410-4
29274 51710-4 31933 128010-3
29304 55310-4 31283 777810-4
30333 74110-4 32393 177510-3
a from K and Raaz [6T K p kPa
63019 101325 63219 101325
48
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Mayer [69] T K p kPa T K p kPa T K p kPa
26216 62710-6 27245 24510-5 29584 21510-4
26326 77310-6 27275 24910-5 29684 23710-4
29814 25910-4
26146 61310-6
26216 68010-6
26276 74710-6
26316 81310-6
26446 94710-6
26486 10110-5
279 5 52 10-5 26546 11110-5
27140 20910-5 28094 58810-5 26566 11210-5
28229 65210-5 26656 12910-5
2 2 28324 71510-5 26755 15110-5
2 28404 78110-5 26775 14710-5
3 28494 85210-5 26975 18110-5
3 28604 94710-5 27235 23610-5
27700 39210 28704 10310-4 27295 25210-5
-5 28814 11310-4 27315 25510-5
2 4 28924 12510-4 27315 25610-5
29034 13610-4 27335 26010-5
29134 14810-4 27385 27210-5
29244 16110-4 27445 29210-5
28324 71710 29374 17910-4 27505 30310-5
-5 29454 19110-4 27575 34410-5
2 1 2 27675 37610-5
27695 38810-5
27795 42910-5
Dat cLeod
26466 92010-6 27345 26710-5
26566 10410-5 27385 27610-5
26665 11510-5 27465 29910-5
26765 12910-5 27575 34810-5
26855 14810-5 27670 39110-5
26895 15310-5 27765 42510-5
26960 16510-5 27875 48710-5
27045 18510-5 7 7
27225 23210-5
7310 5910-5
27320 5910-5
27465 0110-5
27605 5110-5
-5
27810 440107805 4010-5
27930 44910-5
28084 57610-5
28079 57610-5
-5
28554 901108804 1310-4 9574 20810-4
28994 13210-4 29254 16110-4
27200 23110-5 29389 18010-4
a from M [70] T K p kPa
29314 0000765
49
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Menzies [40 94] T K p kPa T K p kPa T K p kPa
39492 1105210-1 60272 60942101 64554 102133664 3 -1 6 6 1 6 102
1 2
2
2
6 682 19012102
6 705 22335102
101 62506 93022101 67994 23255102
1 97609 1 68343 102
5 2 1 6 9 1 3 102
1 2 02
2
10 02 2
1 2 2
1 2
Dat illar [7
2310 735710 0701 639610 6514 1478146458 7359 61105 71667101 65674 161401052692 10943101 61566 78228101 65945 168731053329 12911101 61997 84660101 66235 176801053710 14201101 62057 85622101 654092 15604101 62495 93023101 754475 1714154861 1880510
264110 62766
10970010
24629271595653 2879 6899
56597 28103101 63013 020510 69287 28342157123 31592101 63054 10256102 69929 311211057763 36429101 63386 8921 70678 346531058362 41294101 63524 115110 70747 349881058720 44652101 63843 180910 59951 57186101 64134 12434102
a from M 1] T K p kPa T K p kPa
46830 1960 57533 3449101
51802 8319 61304 7475101
61394 7605101
Dat orley [
p
57193 3264101
a from M 72] T K kPa T K p kPa
28914 1 -4 13310 32313 5110-3
30313 3 333 2 285 -3
-4 53910-3
Data urgules opor [73]
6010-4 1 1031313 69310 34312
from M cu and T T K p kPa T K p kPa
46565 191 53217 127101
47615 257 54658 1808101
48516 336 54958 193 101
49416 444 55918 2438101
50757 663
3
50
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Neumann and Voumllker [74] T K p kPa T K p kPa
34382 68 -38110 31198 73210-4
33882 50 -3
39 -3
32
32533 196410-3 29779 25610-4
29639 19610-4
3 1 2 11
88 -4
Dat dder and tt [75]
p
0510 30913 60310-4
33562 5610 30633 49110-4
33402 55710-3 30563 45710-4
32938 59710-3 30038 29910-4
32123 144810-3 1953 3110-3 9404 7910-4
31693 10910-3 28954 2010-4
31408 410
a from Pe BarraT K kPa
55668 2249 55718 2261 57318 3313
Dat aundler [
p a from Pf 76]
T K kPa28814 10 -4801032943 24 -3
35 -2
ata from Poindexter [77]
T K p kPa
011037192 0710
DT K p kPa
2 1 2 13534 8410-7 6744 3410-5
24044 36310-7 26917 1 -5
4 -7 2 -5
7 -7 2 -5
1 -6
2 -6 7 -5
3 -6 9 -5
6 -6 1 -4
19358 40010-10 21631 69110-9
22330 31610-8
2 5 22 916 -9 1 -7
6 -9 1 P triple p ot included in analys
651024220 9510 27336 521024503 6010 27491 921025043 5610 28113 57610-5
25260 3410 28400 711025594 2810 28618 611026116 9510 29287 611026235 78610-6
20325 80010-10
0630 3310-9 975 7510-8
20947 910 23038 001021543 4710 23139 1410-7
oint below oint n is
51
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Dat amsay and Young [36]
a from R
T K p kPa T K p kPa T K p kPa 49531 459 63067 10244102 63187 10106102
54398 16579101 63067 10223102 7 7
Dat egnaul
2046 38622102
55338 20952101 63246 10240102 2146 38723102
63165 10260102 63246 10214102 63165 10269102 63187 10181102
a from R t [33] T K p kPa T K p kPa T K p kPa
29671 90710-3 47365 2934 62779 10109102
31114 13110-2 63166 1022102 6 7 7 7 7 78208 9319310
37372 74710 60479 64836101 77342 79543102
61808 83313101 62779 10109102
45104 1429 6 1 2 Da debu n [79]
8634 20393102
37372 74010-2 52425 988 0177 35813102
29852 45310-3 52577 104101 1751 42405102
32228 11610-2 52862 113101 4924 61513102
34586 24410-2 57039 31781101 8522 97548102
37323 54310-2 58725 46103101 2
-2
41943 46110-1
2802 015710
ta from Ro sh and DixoT K p kPa T K p kPa
44354 83910-1 46275 1644 45124 111 47035 2104 45325 117 47595 2520
Dat oeder a ietz [80]
T K p kPa
45705 1351
a from R nd MorawT K p kPa
41313 243310-1 52317 9930 43314 546610-1 56318 2646101
19 7363101
48316 3160 45315 1187 613
52
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Ruff and Bergdahl [81] TT K p kPa T K p kPa K p kPa
47815 16 57318 291101 62519 101102
50817 43 58318 423101 6
Dat hmahl Barthel and Kaloff [82]
T K p kPa
3019 101102
51317 47 59719 504101 53317 12101 61519 687101 54318 13101 62819 100102
a from ScT K p kPa T K p kPa
44664 9310-1 51917 892 61769 8121101
44964 10 52917 115101 62119 8765101
47815 272 53167 125101 62819 9806101
47966 284 54068 1540101 62969 1010102
48216 304 54968 1919101 63718 1148102
48766 360 55168 2034101 63968 1211102
49266 423 56268 2604101 41243 23710-1
49366 436 57268 3260101 41533 26910-1
49866 499 57418 3350101 42043 33210-1
49866 507 57918 3746101 42564 41510-1
49916 513 58268 4041101 43064 50310-1
50416 584 59619 5313101 43554 60310-1
50717 636 60619 6467101 43864 68110-1
50967 697 60919 6819101 51067 697 61669 7923101
Data from Schneider and Schupp [83]
T K p kPa T K p kPa T K p kPa 53968 1484101 50016 55018 1943101531 51917 800 49116 400 55218 2038101
48416 295 55318 2024101
51817 788 52317 101101 55418 2190101
50116 537 54518 1727101
50216 521 56318 2686101
16 507 55018 1933101
57518 3468101 55118 1993101
Data choumlnherr nsel [84] p a
51917 793
52167 905 51917 881 51967 967 502
from S and HeT K kPa T K p kP T K p kPa
105144 90 158199 991 171640 1490 118624 200 163252 1155 172605 1535 132214 382 166597 1275 173551 1575 142466 571 168668 1345 151037 782 170476 1430
Data from Scott [85]
T K p kPa 29314 17310-4
53
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
Data from Shpilrsquorain and Nikanorov [86] T K p kPa T K p kPa T K p kPa
55411 2152101 63561 1123102 78677 96252102
56061 2505101 63981 1210102 79686 10798103
56711 2893101 64211 1257102 81446 13057103
57891 3740101 64381 1293102 83625 163551103
60061 5854101 66430 18254102 80366 116117103
60411 6261101 70729 34921102 81546 131973103
62111 8635101 74278 56147102 82245 142302103
62221 8811101 75598 66372102 83185 156996103
62371 9038101 77467 83905102 84539 179551103
62681 9547101 64801 13862102 84724 182505103
62941 1002102 67730 22531102 85454 196728103
63521 1117102 68150 23779102 85644 199968103
64331 1279102 69470 29070102 86664 221186103
61971 8419101 72409 44107102 88043 251478103
62811 9815101 73239 49111102 88213 255352103
62831 9889101 75268 63837102 88323 257295103
63091 1034102 77457 83449102 Data from Spedding and Dye [87]
T K p kPa T K p kPa T K p kPa 533825 1306101 573610 33293101 613886 75568101
549811 19337101 586013 43390101 620254 85144101
558948 23954101 594741 51918101 630244 10222102
564721 27351101 597253 54588101 565743 27964101 604288 62792101
Data from Stock and Zimmermann [88]
T K p kPa 28314 73310-5
27315 23910-5
25317 44010-6
21319 65310-7
Point below triple point not included in analysis Data from Sugawara Sato and Minamiyama [9]
T K p kPa T K p kPa T K p kPa 60167 60389101 73522 52093102 87315 23650103
63083 10258102 76875 79022102 89271 28647103
66410 18162102 79555 10710103 91861 35883103
68399 24860102 82415 14651103 92962 38828103
70503 33804102 85324 19858103
54
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
55
Data from van der Plaats [89] T K p kPa T K p kPa T K p kPa
27315 62710 P
-4P 28714 13210P
-3P 28914 15310 P
-3P
28314 10710 P
-3P 28015 94710P
-4P 28614 13310 P
-3P
28714 13310 P
-3P 28314 10610P
-3P 28614 12510 P
-3P
28514 13510 P
-3P 28314 11210P
-3P 28714 13510 P
-3P
29114 17710 P
-3P 27315 64010P
-4P
27315 56010P
-4P 29214 17210P
-3P
27715 77310P
-4P 27315 58710P
-4P
28214 97310P
-4P 28414 11110P
-3P
28314 10310P
-3P 35412 14910P
-2P
27315 68710P
-4P 35812 16610P
-2P
29314 17710P
-3P 28514 77310P
-4P
Data from Villiers [90]
T K p kPa T K p kPa T K p kPa 33312 34710 P
-3P 37312 40010P
-2P 36512 25510P
-2P
34112 57310 P
-3P 33312 36710 P
-3P 37312 40110P
-2P
34912 10110 P
-2P 34112 58710 P
-3P
35712 16410P
-2P 34912 10310 P
-2P
36512 25710P
-2P 35712 16410 P
-2P
Data from Volmer and Kirchhoff [91]
T K p kPa T K p kPa 31293 829310 P
-4P 30863 593410 P
-4P
31293 817510 P
-4P 30863 599010 P
-4P
30333 404810 P
-4P 30863 600010 P
-4P
30333 395710 P
-4P 31293 825710 P
-4P
30333 396010 P
-4P 31293 821110 P
-4P
Data from von Halban [92]
T K p kPa 25516 37610 P
-6P
21979 33110 P
-8P
Point below triple point not included in analysis Data from Young [93]
T K p kPa T K p kPa T K p kPa 45695 133 49531 459 62995 101310P
2P
45685 131 51012 691 71660 386210P
2P
51007 6913 54348 165810P
1P 71760 387210 P
2P
45690 132 55338 209510P
1P
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
56
Appendix B Detailed Listing of Supplemental Experimental Data for the Heat Capacity of Mercury
All temperatures have been converted to ITS-90 Data are arranged alphabetically by first
author Smoothed data from Amitin Lebedeva and Paukov [123]
T K C BpB J(molK) T K C BpB J(molK) 2343375 28543 2899958 27987 2400066 28473 2981437 27911 2500049 28359 2999932 27899 2600029 28255 2700007 28162 2731500 28134 2799984 28076
Smoothed data from Busey and Giauque [44]
T K C BpB J(molK) T K C Bp B J(molK) 2343206 28476 3499729 27606 2400264 28430 3999785 27359 2500185 28351 4499942 27204 2600103 28275 5000132 27129 2700024 28196 5500289 27117 2799953 28121 6000361 27146 2899893 28041 6500326 27217 2981452 27983 7000199 27338 2999843 27966 7500049 27514
Note Maximum temperature of their measurements was 330 K values at higher temperatures are based on measurements in the literature Smoothed data from Douglas et al [51]
T K C BpB J(molK) T K C Bp B J(molK) 2343006 28275 5131679 27158 253166 28147 5331743 27141 27315 28019 5531796 27132
2931376 27900 5731835 27130 2981352 27872 5931858 27137 3131293 27790 6131863 27150 3331245 27688 6297653 27167 3531229 27595 633185 27171 3731238 27511 653182 27198 393127 27435 6731776 27232 4131319 27368 693172 27274 4331382 27309 7131658 27321 4531454 27259 7331596 27374 473153 27217 7531541 27433 4931607 27183 7731501 27499
