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Calhoun: The NPS Institutional Archive
Theses and Dissertations Thesis Collection
1952-05
I. Integrated intensity measurements for
vibration-rotation bands of carbon dioxide ; II. Total
absorptivity measurements on carbon dioxide at
room temperature.
Holm, Robert J.
California Institute of Technology
http://hdl.handle.net/10945/24737
JK]:^[iGEA,TIH:D I]Nf'ni:N:3ITY MEA-SIJEEMENTSi:^Oj[l VElMlATIQN4lOTA;nON B/!uNDS OF
CARBON DIOXIDEIL
TOTAL ABSOIlPTIVin' MEASUREMENTSON CARBON DIOXIDE AT ROOM
TEMPERATURB
E. J. HOLM
JiWiii
Library
U. S. Naval Postgraduate School
Monterey, California
I. IH?IB<»AT13D INTSHSITT F!a^.3UESrC3I?S FOB TIBE^TIOB-
^ HOTATKSI SAJTDS OF CAEBQH DIOXIUB
II. TOTAL ASSOHiTITITy M7ASUH3^GSTS 02T CAK30N" DI0XII3S
AT BOOM T5S1PIIHA7UHS
fhesis "bgr
Ro^rt J. Sola
Lleatenant Colonel, United States Marine Corps
Zn Partial Tulfillnont of the Requiremonte
Tot the Degree of
Aeronautical 2n^neer
Galifomia Institute of iPdohnologsr
Pasadena, California
1953
UTiesis-
^
1
The aathor wishes to e:xtend his appreciation to
Br. S. S. Tenner, under "s^ae direction this ^rk
vaa conducted« ssul to Mr* D. Weher for help ^flth the
«3Qp6rlmental \tfOx4c*
18037
11
ABSTMOT
I. !!!hls study contains an outline of the dxperlnsntal
aaasurenenta perforE^d in order to determine integrated Intenaltiea
of Tarloos vibration-rotation bands of csarbon dlosdde "by use of
standard teohniciaes ^^th a Peikin»:3Lmdr apeotrooeter*
IZ« ^tal absorptirlty neasaremants on carbon dio3:lds %t
Tocm t^aperatares were ri^de in a pressurized gas cell provided with
transparent windows*
ill
7ABLZ 07 OCmmTB
Acknowled^^nents i
Abstract 11
^"ble of Cont^its 111
Table of figures Ir
^jnxibols ^ri
!• Integrated Intorislty Mnagoromanta on Oarbon Dioald© 1
A. Introcluction and Sosisaxy X
B. Methods Vtv th© Hxpericwmtal Deteraination of
Integrated Intensities 2
0. lilxperiraemtal Sto^loa 6
D, Coaparison With 'Phe RGsnlta of Other InTestigatora 7
3, Calibration of Perfcln-HLmsr SjjectroraGtey idth
Sodlun Chloride Prlaa 9
II, i\>tal AbaorptlTity Maasurojaonts on Carbon Dioxide
At Boom Hex^geT&imre 10
A« Introdeletion and duiamaxsr 10
B. Basic Hadlation Laws 13
0, IBotal Absorptivity Detonainatlona On Carbon
Dioxide at Boora Teraperature 15
D. Coniparison with the Reaulte of Other Investigatorg 19
i
IV
Tlsar© HtlQ Page
X* Schesatic Representation of Infrared AbsorptionCell Used to Measure Intensities of Qe.a Kixturea 22
2, ^/2,303 aa a fsmc tlon of pi" for the CO., bandwith a^mter at 5109 en . -
''
«< := .426 •*• ,043 gq"^ - atn"*"^ at 290 K. (S.57 cmcell Itmgth, p„ c 90 paia) 23
3» /2.303 aa a fttficticn of p^f for the OOp bandwith Gonter at 4983 ckT^.oC= 1.01 + ,10 cra~2 . ato"^ at 298°K.(3.57 ca.
cell length, p» = 500 paia) 24
4. p /2.303 a3 a fanction of p^ for tho OO2 l;>aad
with centor at 4860 00*^.
<<!= .273 4- .037 cs"- - &tEr^ at 298®K. (3.57 cacell lengl!i, i>j « 500 psia) 25
6* ^/3.303 aa a function of pi for the 00^ t^dud
ulth oQQter at 3716 ca*"^. .
oC e 42.Z -¥ 4.33 ca^^ - ata*^ at 29B K. (.5 oncoll leue^ P^ « 500 p3ta) 36
6. p /3.303 aa a function of pi for the OO3 bandwith canter at 3609 CQ**^.
dJ.« 28.50 ^ 3.85 cm--' - ^tra""'- at 298 K, (.5 mcell length, pj « 500 psla) 27
7. ^ /2.30s as a function of p-f for the OO2 bandwith cantor at /'334S cm*"^.
d. e 2706 "fr 270 gbT'' - atm*^ at 208®IC. (5.15 mcell lengflh* p^ « 700 psla) 28
8. ^/2.303 aa a flmction of p^ for OOg in theregion bet'^/eon 3000 ^d 3150 oq-^,oc = .147 -}• .047 CB*'^ - atn-^ at 298 E. (3.57 end6.72 en cell len^^, p^ = 500 paia) 39
9. p /3.303 aa a function of pi for OOg in theregion between 1800 and 3000 oa"^.•C « .083 t -OOQ «a-2 . ata"^ at 298®K. (6.72 mcell length, p^ » 400 pala) 30
i
'EASL& OF FIG0K3S (Cont'd)
n^OLT&n ' TitlQ Page
10, /5/;3«308 as a fmiction of pi for OOp bandwith centsr at 668 ca"^ Including veSk nai^^jhTjor-
ing bands with caitera at 720, 667 and 618 ca .
ot = 171,6 + 17.1 co'^ - eto"^ St 298^.(1.986 em cell length, p>j, » 600 psia) 31
11. Calibration wmro for infrared spectronsterwith HftC/ prism 32
13. Calibration ctirvo for infrared ffpeotroaaterwith HaCi rrian
'
33
13. Hlodk: diagx^m of aj-tparatua for laBafirajremisait oftotal ab3ort:tloa of infrared radiation 34
14. Ab3orp»tivlty ^ as a function of Pr, for variouafractional prosaures of OOg at room'^taar>erattire.
(The OO2 waa pressiiriaod with nitro^^^i) 35
15. Abswrptivi^ c< as a ftmctlon of pi for 00^at room teRtperator© and a total pressure ofone attaosphere 36
16. Absorptivity oC aa a function of pi for COgat rooHj tepiperature and a total pressure of oneatnosrher© 37
17. Absorptivi^ ^ of OO2 at roois teKparature aaa function of pi at various total pressures 38
18. toaparison of e3$>eriniont2lly determinedabsorptivities as a function of optical densityfor OOp at atriiosplaerio pressure and roootonrperatore with the results of studies carriedout bgr £k>ttel and Man^lsdorf 39
19. Oonparison of eaperiaentallj'' dot 3rainedabsorptivitiea as a function of optical densityfor obg at atnmspharie pressure and rowsteriperattrre with the results of studies carriedout by Hottel and Hangelsdorf 40
i
eL s; Int^ratod intenai^
^\Pta. apectral absorption ccefficiant
KX) cs wave zsoaber
V S£ qn/mttas nom'ber
»w S transsltted intensltar
^ou;b: incident Intensity
P vs. partial pressare
i = optical patli length
5Jo«; s apparent lnt«aialty wltJmut absorber
^u;B apparent intensll^ with absorber
la apparent integrated Intensity
P «e pi/oi'
Pf ae total pressors
T tB ralcpoaetor screw tozns
B as defined spGotrcsaeter oonatant
^2 SE Itsstrahlan ware manber
pje SB optical densitsr
Paff^ »H. » onexigy omitted by a blackbo^ at toraperature 5? at'^ wave length /\
R » Mierigy emitted by a blaokbody at teini^ratare H atware ntmber tu
i
iI
I
I
vli
STfSOLS (Cont'd)
7\ « vav© longth
Oi - iia-ro mmber
<^1'«2 ta. physical conetaate
c s velocity of light
h «e Pleaek's constant
k tc Bolt!S'!Vum*e constant
T - absolute tem^^eralture
a- m Stsphan Boltxnann constant
i SB eiaisaiTlty
»u,B spectral intensity of ssdssion fron greybody
•^ t« engineering enissivity
I as recorder constant
K« s defined recorder constant
2) s recorder deflection
«(. s absorptivity
^is globar tfflnperature
i
I. imrmATmi xhtshsitt mmsohsmbnts oh ciiKBaif Dio3ciia
A> Introduction f^r^*] i^-iff^iy
The Iraportanca of gaa radiation in effecting haat transfer "be-
tween a gaa and Its surroundings, particularly when the gaa temperature
is hi^, has l>een recognized for son» time. Hovever, accurate
eBlsaivit^ data are generally not arallable for use in engineering
calculations of heat transfer. Recently atterrpts hare been made to
calculate gas enissivities theoretically from spectroscopic data.
It is the purpose of the present stucly to provide some of the basic
data \<>hlch ar© needed for the theoretloel ca3,Gulation of esiisgivltiet
of carbon dioslde.
Qp.antitatlve infrared int^isity raeasurenents haye been carried
out for tlie more intense vibration-rotation bands of carbon dioxide
using helitasi as a pressurizing agent. Measurements vere made I7
use of standard techniques. The results are susiaarlsed in !rable I.
gable ^. Observed Integrated latengitiea* of oarbon DioadLde
Band Oenter(cm-i)
Integrated Band Center Integrated
(cn"^ IntensityIntansilQr
(cm^ atm"""^at 298°K) (c5^ atE'^at 298**K)
5109 .43^^^^l combined .831886)4983 1.01
4860 .37 730)3716 42.30 668) combined 171.503609 38.50 647)3349 2706.00 518)2137)3CD4) combined .1472074)
-^-- -.'. -t. ."! ..i.'ti'.iiiir ur,".'i . i"i . : 1 1 ,i. rs:a';-7y:
" 0^:53erv9d intoasities are accurate v/ithin + 20^,
-3-
Integrated i&tenaltiea of the infsrarod vibration-rotation bands
are retgoiired for the theoretical oelcolation of gas enissivities and
radiant heat transfer.
Qie integrated intensi^ ^ for a given Tibr^tion-rotation l>and
is defined "by the relation
/P d CA/ (1)U/
vhere P repreeents the spectral absozption coefficient at the
varre nual^er u> • Although the limits of integration should ext^oid
from - flo tc •* oo it is sufficient to restrict integration to a
Barrow vave nosber InterTal bracketing the band center because P^
decreases very rapidly with <JJ In the wings of the vibretion-rota-
tion uands* The integrated intensities for various yibrationp>rot8F*
tioot bands will be idraitified by appropriate changes in yibratiomal
quantUB noBiber. Tor esasaplQ^ the intaaae V - fundamental of
(2)carbon dioxide arises as a result of the ti*aaaition*^ '
T- a= 0->r- « 0, Tp s= 0-»Vp = 0, i'lss O-f-f e 0, Tg = O -? Vg - 1
and has a band center at 2349*3 cbT^. 9he corresponding value of
the integrated intaisiV i^ ^^^^^ identified by the symbol
• For details concerning spectroscopic notation of polyatomicnoleoules see, for exanple* G. Hersbex)
Sneetra. D. Van Ho strand Co., He-^f Toiknoleoules see, for exanple, G. Hersberg* Infrared yI'^^ r^fffWW
(1945).
I
-3-
oC (0,0?0 -S) 0,0?1)
The integrated intonaltles of other vibration-rotation bands tas^
be identified similarly,
(2)a) Ihe Method of Wilson and Wells
Tor laonoohroQatic radiation it is well knovn that
lu, « low «a^(-^oi P'^^ ^^>
^ere I ^ is the transmitted intensity at the vave number Uf
«?hen the incident intensity is Iq^ t P is the partial pressure
of the a"bsorl5ing |^s ?Jid J? repres^mts tlie optlcid path length,
Honoe the intof^rated intensity beconiea
oC « {vif^ JU dotu / Jo, ) d u^ (3)
where the integration in Sq, (3) is to bo performed over the entire
effective width 4U> of the vibration-rot?ition band under study.
The apparent intensities observed ^thout absorber and with
absorber, when the instrunont is set at cu , are not I^^^ and 1^
respectively, bat rather
and
2«,.. = / I„_' g(u;, w/») du^« (4)
"^ijj~ I I^' g(a>,a/«) du;« (5)
i
-4-
where ei^ * ct;*) rerpraaeata ths frpctioa of li^t of actoial imvo
aoaber uf* to which the Instroaont resrponda when it ia set &% uJ »
Soma of tho difficulties inherent in the ealGolatlon of P^ do
aot arise in tho dotermination of tli© integrated Intensity. FroQ
ea^eriiasntall^ determined v: lues of T^ and 5?^ ^^ it is
poasible to detasralna an apparent integrated Intensity «< • ^Ich
is defined tiy the relation
ivt f^/^Jn (Too,/ 5^ ) dtu« A/p^ (6)
(3)VtlaoBL and W^Xfl have 8ho\m that
when a number of specified conrJltiona are raat. Ihose ooadltiona
includa the requli^ment ttiat X^^, he independent of uu in the
r©»ol7«d speotral rssnr^o, a oondltion which can "be approached closely
lay eliminating atnoapherlo aheorption and ualag aofflciantly narrow
spectroraetar alits to gire hl^ epects^ rosolution. In addition to
requiring oonst^mt T^^; • '^'^* ^^^ ^"^^ ^^-^^ ^^"^ ^^ either the
variation of P with uj oan be neglected In the spectral range
or the resolution of the Instrwaent does aot vasy appreciably over
the vibratlon^rotatlon band under study* Of these two requirements
the latter conatltutea m, intrinsic proi^erty of the inatrumont. 2ho
varlatlorx of P In the resolved spootral interval can bo mlniiaiaed
1)7 presflure broadening, i.e., as p </ is decreased, eC^ will
apfproaoh «C more rapidly, the higher the constant total presaare
at which the ottsenrations are made*
As the optical denalty Is decreased, the plot of ^ rs p*/
WB^ show considerahle corrature. This fact introdjoces an appreoial)l6
error into the extrapolation required to determine ^ • At
sufficiently hi^ total presatLre j>^, the Yarlation of p with, p-^
ahoisld follow a linear r^atlon in accord with the fact that the
true integratsd IntGnal^ is neasured at every -teIub of the optical
density and !3q., (6) ^lOiHd apply directly. By proceeding according^
(3)to Wilson and Wells ^ the result oC •—> ^ as p^ is Increased
(3)can be demonstrated* '
The true value of the integrated intensity o< con be obtained
either by ©rtrapolatinc *C' *o ssro 7a3.ae8 of p>P at constant
Pfp or by flndii^ the limiting value of c<. • at constant optical
density as the total pressure is increased.
V (4)"b; fhe Self-Broadening Techniqae of Penner and Weber
Infrared transmission studies on pure ^ases have the obvious
advantage of eliminating the ijossibility of ertjeriiaental error
resulting from liaporfect mixing or ftori the occurrence of adsorption-
dosorption phenomena, to the other hand, they possess the sever©
diMbdvantage of alw^s involving the effect of si^ificant self-
broadening associated with increased pressure of the absorber, xlo^^
-6-
errer, liy atiltable cholca of t©3t cell langUh It ia possible to
utilise 39lf-broadenliv; to oTjtala cjoantitatlve infrared inteaaity
data* In genaraly ths required call length la aborter when thQ
.ll)ratlon-rotatioa band la laoro Intense,
a) Apparatna
A Perkin-Slmgr Model ISC single "beam Infrared apeotrwaeter
>fith llthluB fluoride, aodloia chloride, and potaaaioB "bronids priama
wsa uaed for transmiaaion meaaureaonts* XnGorix>ration of autoc^tio
allt drive over the wavelength Interpol used for 8ta<^ was found to
save conaiderahlG time In esiperlsjontal vioife, Preaaure readings were
perfoaaraed 'ogr uae of a 'r/allaco and Tleman prodaion maionieter for
the preaaure ran^e 0-800 ess of mercury ( ± ,2 an) and 0-1000 palg "by
uae of a liarah gege ( ± 2 paig).
!I!he 0^1 and window asaeabliea were nachlned from 18*6 atain-
leaa steel stock. Heoprene 0-rin^s and neopreno or teflon gaskets
wore uaed to support the C5«ll windows, 'Bi© principal features of the
cell Bve aho^a in Tig. !• ^e ri^t end plate ia provided ivith a
special tap to pemlt flushing with nitrogen of the outside of the
cell in the li^t path. ^Is tame end plate la fitted with a
flange to slide into the absorption cell slot provided on the spectro-
meter. A flexible collar ia inserted between the other end plats
and the globar source. Bie collar alao has a fitting for nitrogen
flushing.
-7-
Th© cell Is provided with a window assaeil^ly bs aliown and ia
large enou^ to pettiait inooxporatloR of atlrrtn^ rod with
perforated end plate. In esvch esperli^Bnt care \ras taken to ass&re
tuaifors olxlng of gates in the cell lay adequate use of the stirrer,
Zt was assumed that a unifozn gas £dztare had been obtained ^tieei
additional stirring produced no sieasorable change in transmission.
Details of %ravel©neth calibration of the prism spectroneter
using a todivBst chloridis pris&i are giv^ In Section S«
b) SoBsmaxy of BaQ^erijaGntal Data
Jbr the ibratlon-rotation bands of carbon dloxiajs on which
experioental meaaure^asnts were peifosaed the qa'snti^ p /2-303
has be«i jOLotted as a function ef p Ji in Figs. 2 to 10. Gorresrjondr
ing integrated intensities hsive been given previously in Table Z.
The observed Inteaisitlss of vibration-rotation bends of carbon
dioxide are ooi^pared with the results of other investigators in
^Rable ZZ. Heferenoe to Table ZZ shows that the data ars in excell^it
agreaaent with the results of other investigators.
-8-
T&ble II. Observed Intensities of Carbon Oioxlda
Integrateid Intensitgr 0C(oa^ atm-^ at 2980k)
Band Caater V/ilBon Sggera and Present(cffl--*-) &% al '^•*^»® Crawford ^^^
Study(1941) ;f 10^ ^ 3SI
.^^951) OSSSl
5109 .426
4983 1.014860 .272
3716 39.0 42.33614 37.0 28.52349 2867.0 2693.0 2706.02137 \3094 V combined .147
2074 0.14 (P and q) )
2074 .06 (qonly)1933 .005 \combined -083
1886 J
720 1668 187.0 161.0 [combined 171.5647 J618
-9-
S« Calibration of Parltin-T^liaer SpQCtjwaeter v/ith Sodion Chloride
In th« ware number calibration of en Infrared spectrometer It
may become necessary to naka ase of the relation betveen laioromater
•orev turns and %;aye ntsuber in t^aye nunber regiions where no
calibration points (absorption bands or lines) exist or ars ayailable.
In the present calibration it was necessary to extrapolate the
aicroneter screw turns vs. wbtq number corre fron the carbon dioxide
band at 667 <m to regions near the absori'tion lirait of the sodiua
chloride prisii, This was done using the aetiiod of KcKlnney and
(8)Triedel. whose ej^^irical equation is
T« 5q - B (tA// -w^r^ (7)
where 7 is micrometer screw turns and ^ is the ordinate intercept
2 2-1at BCiWo"' - u/ ) =0, Here W-r, i* *he Eestrahlen wave number
depending on the isrisa material and u> is a kno'^n or measured wave
noiber. Seren absorption laaxlria of asasonia and carbon dioxide were
3 2-1used for calibration and (uJ -ul") was calculated and plotted
3
a^lnst micrometer screw turns* For sodium chloride the value of
tti is 125 cm" .
She constants ? and B are determined from the known absorption
maxima. Sqoation (7) is used to extend the calibration curve of ? vs
UJ , The correction terra for short wj^^ve length absorption was
neglected for the present purpose. Figures 11 and 12 are reproductions
I
I
-10-
of original calibration graphs in ^ich the abscissae are,
2 2 *"1
respectively, UJ and (u/g - Uf'^) , ^eroas e^ch ortUnate rep-
resents alcpometer screw turns.
-11-
IX, TOTAL ABsoHPTiviCT 1 irAsiHc^-SKTs OK CAHBOJ: mcxiw>AT BOOM ?3JU^HA7USE
A. Introduction and 9ugnBary
ThB calcrilation of radiant heat transfer from heated cai^hon
diosiidG requires the use of experlraontelly detorralned abso nativity
datti. The total a"b3orption of radiation hgr carbon dioxide has
been reinvestigated at various optical densitlca at different total
pyeasures and at room temperature, A complete investigation could
not ba carried out at other temperatures because of erperii^ntal
difficulties with the gaa cell and aE^lif^ing aysteEi. She measured
values of the total absorptivitiea are given in fteble III,
-13-
5s
«H
1^
II
« o
O T<
Q
3r^
JO O
A P.
MM
II
Pi a *—
•
5 ^
li
4: J
8 ^ «5
Its ^
8 ^ ^
S ^
P« 52, w*
O
p. a. '*—
o >5
(I
0* o, «>-'
0)
i!
OO OiHiHr-IHiHCMCV
H >T E^O^ -*^ O\0 •-• •<*
f-i
iigfg^g
SS^ii^Offi• • • • •
cv
O O O O O O fH
O M\
O rH H WcAt>-0• ••••••H
SS««S8g
• • • • • •
N m r-o o o o O C5 c
c^^**^^ to tf>
o o o o o
• ••••••••iH C\i <^ -^tA
-13-
The spectral distribatlon of radiation from a blackbody is
(9)given by Planck'a radiation lav
-5 r i'^R^ d/^ « c^^ ^ [axp (c^/i^ f ) - y d>^ (7)
vhere H. d^ is the energy ositted from a blackboi^ at te:i^eratare
7 per unit tioe per imit area in the wave length interval from A
to ?i plus d^ thron^ioat a eolid anglo 2 W ster^idians. e^
and c^ are phgrsioal constants whose raloea are given belows ^ '
? —5 ?« 2 IT oh « (3.732 + ,006) x 10 erg cm aeoj
(jg « ch/k « (1.436 t .001) cm \\
-10 -1c =3 velocity 0^ li^t «= (2.99778 ^ .00020) x 10 ca sec {
h ax Planck* B constant « 6.62 x 10 "^^ erg aecj
-16 -1k SB 3oltznann»3 constant =* 1.381 x 10 eisga par nolecal© E ,
-1
Bquation (7) aay he expressed in terras of wave number ow C- ') )j
E^ d^^ =s Cj^O^^ jTexj. (e^U#/T) - ^ du> (8)
iriief« E dtu is the enefigy eaitted from a "blackbodiy at terrrr^ei*-
tare T per unit time per unit area in the wave naaber interval fr<»i
OU to u; plus du> thj^u^out a solid angle S fT steradians.
•14-
The total intensity of radiation oiaitted Toy a blackl>odgr over
all wave lengths is glrsn by Stephan'a law
R ^. d o; = C7-T^ (9)
o
where <?" rer:)resents the Stephan-BoltsBJiaaa constant and has tho
numerical ralue^"^*^' (5.67283 t .0037) s lo"^ org cn"^
^ sec (= 2 7r^ /I60I1"), Jtey a sresrboasr the eslsaivity £" l3
Independent of wave nonber, i«e«t
lAore ^/r) ' ^3 the apeotrsd intensity of radir^.tion emitted from &
gr^'ooay. The enginoerlas endasivity or aTjsojpptivitgr for diatoiaio aad
polyatomic ^ses is defined t^ a relation similar to ."^tx* (9), 5!hn8,
if 2 is the 3::>Gctrally eaaitted intensity from a non-black and a
non-grey souroo, then the engineering eriisaivity B I3 given ly
CD
»« j(l^l CTlf^^UJ (11)
O
%diere I^ is R^^fi - oxp (-r^ yi ^ , Pj^ Is the sx^eotnal
absorption coefficient and ^X 43 *^ optlcasl path daaalV"
Equation (11) can be ^/rltten laore e^^jlicltXy ae a ana over tha
contributiona to the total emisaivlty fsom aexiarate vibration- rotation
bands, ^has, let,
/^\X) ss ^CjJ (vj^, Vgt Tg -r* v^, V3, Vg) r^Fesent the effective
-15-
\/idth of the ibx^itlooF-rotation band arising from the trausltion
X (-'Vf f i i .f i £ 4(13)
ighex^ the qtttattm zma'bers imat conform to the aelaction snlea for
aXI allowed ribratloiial transitions* QaantitatiTe calcolations of
:? ara eocoeediixgly difficult to cariy out.
Jto i^iponatua hag "beati 'Dalit for the oeasareaeat of abgorptirity
and eniasivity of carbon diosido* u!ha ssraten consi3ta of a aouros
of inf1raa?ed radiation, a gaa cell in which tenperatore and preasure
ay be controlled and a noa-aelective receiver, 2ie signal from the
reoeivdr or detector la aztpllfled oaing chopped radiation for
stabilisation. The percental of transiaiasion is found 1:^ conrparlng
volta^ outpat from t3ae detector for an oapty cell with voltage
output from the detector for the assae cell under test conditions, A
recording potentioiaoter (3peedonax) is used to indicate volta^. A
block diagram of tho apparatus used for study of absorption and
emission is shown in ?ig» 13.
Tho source of radiation used is a globar unit which has a
continuous emission apectrum in the infrared region.
-16-
The glo'bar teraperature snist be held 'fithln close limits to reduce
fluctuations in radiation. Power empi^ly to the glol>ar is
regulated "b^ a Sola constant volta^ transfomer.
The globar, e^as oellt and (letectin^ thermocouple are placed
in a wooden chamber ^ioh is flushed \fith nitrogen to prev^it light
absorption by atnospherlc water and carbon dioxide, fhe cell ia
fitted with potassium chloride windows \diich allow transnission at
ware lengths longer than 30 microns.
She detector is a thenaocouple which develops a signal of 100
raicrovolts with full globar inimt. Sensitivity of the thercio couple
ia specified as six aicrovolta per microwatt of incident radiation.
This thei^^ocouple is of the aaae tyj^e as that used in the Psrktft-
Haer Model 120 Spectroneter and is reported to be linear in output
over wide variations in lig^t intensity at all wavelengths in tha
near Infrared re^on. The thermocouple is sensitive to anbient
tdoperature changes. Drift and instabili^ prodnoed by such ch^m^a
are avoided by chopping incoming xediation at 13 cycles par second.
Thus a low frequency A.C. ar^^lifior may bo used to ararplify tha veiy
low level signal fron the thermocouple. The A.C. ai^ial is later
rectified and filtered to recover inforniation regarding signal
anplitude. Contacts for the synchronous rectifier are operated "by
means of cams on the shaft of the syAchronoua motor used for the
rotating shutter.
-17^
Salaslvity as v/ell as abaorptlvity rnsy "be measured with this
^79tei3. Wot emlasiyity raeasoreHaenta it la onljr nacessasy to place
tha light chopper disk bat^^een the aauple and the thdrsiocouple
rather thsa between the glohar and the gad sanple*
Since percentage of transmisaion la meastii^ed by noting tho
dlfforenco in radiation Intensitjsr recol-Ted wlien the coll la
e7;),cuated and tho radiation received ^^:i the cell oontalna gas at
kno'vm toiai>Qrature and preaaure, it la injportsint that noaaurementa
he nada within the llaita of Ijjnearlty of tha detecting and anrplifylng
ayat^i. Iliere la no Q&ay moans available for the maaaura'nent of
absolute radlaticaa Intfsnaity received at the thernaocouple, 15m
anipllfiej:' and Speedoaax were found to be linear with rasx)ect to
inpat signala from the detector.
Percentage of absorption by carbon dioxide at tho tenperature
and pressure uaed waa foimd to be of the order of 25'j& or lass. In
order to get reliable data it la noceaaaxy that noise and drift be
low in cornmrlscm '.^th variations in si,(^al strength arising from
changes in abaor^itlon of radiation. Holae and drift in the
Instraraont -i/sro r^dnced to below the IjS level.
(10)Previous invoatleations were carried out at a total pressure
of one atrwaphere while v^jyin;^ tha partial pressure of the absorl^
Ing or radiatlnj^ £^a». Wo have investigated absoriition of radiation
at room temperature at total pressures up to 55 atmospheres.
-18-
Let D =s recorder deflection for the filled gas cell and Dj^ s
th© deflection for the eiapty cell, K ss recorder constant,
Tg » globar toaperatur©, C s"= aniaslvlty of aoaroe,
C7"s Stephan-Boltjcaana constant, pC « ab»orptlTlty and K» « K/Cr^»
Theo.
XDl= <r^,4 (14)
an4f " t, = !•
:• - ijj/a^ (15)
^^en the {^as cell contains a'bsor'bing gas and £. - 1, then
K»D« (1-e^)/, (15)si
•< «= 1 - D/B^ (16)
It follows from Klrchoff^s law that ihe total absorptlril^ as^d
aalssivity of the oar1x>n dioxide are 9.|aal to each other at
eqaili'brifn. At room teii^^erature it lias been aaanmed that the
omission of radiation froa carl}on dioxide is negligitxl^r sioall
compared with the intensitQT of the transmitted incident radiation«
The results of total absorption measorenents are presented in
fables III and 17 and are plotted in Tigs. 14 to 17. !^ble III and
Tig. 14 contain a woaa»xy of the experimental data which wore aotualljr
-19-
o'btalned* ^blo 17 and Tigs. 15 and 16 contain results applicablt
to a total pressure of 1 atEWSpharo, In Fig, 17 the a3>sorptivlt3r
is plotted as a function of optical dcoisiV with the total prossore
pm treated as a rarialile xunxwneter* jReferenoe to Tig, 17 shows
that o^ is not a sensitive fimotlon of the total pressture at
prssscires in exoevs of about 3.73 ata.
f^hle lY. AhsorptiTitsr of CJarbon Dioxide at a Pressure of 1 ataand at Boon fictperatur@
P^(ft-atm) Absorptivity c< (ft-atm) Abaorptivitj?" o(^
10 .221 .4 .081
8 •197 •3 •064
6 .173 .1 ,054
4 •148 .08 ,050
3 .133 .06 ,045
1.8 .113 .04 ,039
1.0 ao3 .03 ,030
•8 .098 .d ,033
»6 •092
<Bie experimeatally determined Talues of c>C at a total
pressure of 1 atm are oonpared wi^ the results of studies carried
(11)out 1^ Hottel and Haagelsdorf in iral>le T and in Tigs. 16 and 19.
I
-20-
Since the Unit of oar probable error is + 10^ and those of Hottel
and Mangeladorf •¥ 305S, the agreen^xt between the Independently
determined experimental data auqr be considered to be satisfactozy.
teble T» Absorptivity of Carbon Dioalde at Sows Tenperature ata Total Pressure of 1 Atmosphere.
Absorptivity oC
pje Hottel and(ft atia) Mangelsdorf Present
(1935) Study
10 •2318 .197 ,
6 .172
4 .17 .148
a .15 .1221.5 .14 .113
1.0 .128 .103
.8 .130 .098
.6 .111 .092
.4 .100 .081
•2 .083 .067
.1 .068 .054
.08 .064 .050
.06 .oe?7 .045
.04 •050 .039
.02 .038 .030
.01 .0385 .022
.008 .0252
.006 .0219
.004 .017
-?>1-
R";^l'R?3y(5SS
!• 0. Harzberg, "Infrared and Baataa Speotra, D. Tan Hostrsind Co.,
Haw To]ric (1945).
2. }^. 3. Wilson, Jr. and A. J. Wdlls, J. Chem. Pfasrs., j^i* ^"^6
(1946).
3. S. S. Penner and D. Wober, J. Chen. Phgrs., lit 607-816 (1951).
4^ 3. S. Peaanor and D. W©l>er, J. Chem. Thya., 2£, 817-818 (1951).
5. A. H. Thomdlko, A. J. *lell9, and 2, B. ^^llson, Jr.,
J. Chem. rtoys. J^g, 157 (1947).
6. A, M. Thomdlke, J. Ohem. Phya. IS, G68 (1947),
7. D. y. /Sggera Jr. and B. L. Crawford, J. Chan. Fhys., ji^^^ 3.^56
(1951).
8. D. S. HcKinnoy and R. A. ?rl©dol, J. Opt. Soc. J\ra. 3§., 223-325(19'i8).
9. I. Pa^'^e, Introduction to fheorotloal Pl^aica., T5. 7^m ?I09tr?nd Go.,New York (1935).
10. A, H. Lowan et al, "Mlacelleneoua Fhyslcal Tables**, WPA ProjectUo. 65-3-97-33. (1941).
11. S. idimidt, Foraeh. Oeb, Ingon. JJ, 57 (1932).H. 0. Hottel and H. 0. Mangoladorf, frana. A. I. Chem. iiaglneering,^ 617 (1935).H. C. Hottel and T. C. Snilth, Trans. A.S.M.Z., ^, 4 (1935).H. C. Hottel and B. B. ^bort, Trmxs, A.S.M.E., ^ r397 (1941),R. B. %bart, Sc, D., Thesis in (Siemical Sogineering, M.I.T.(1941).
-2&-
f^ S
teas
4=?
csj csS-rv ^Xn333v"^-^
ihAa
Fip. 1. Schematic representation of infraredabsorption cell used to measure intensities ofgas mixtures.
-23--•7
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Thesis
H69
18037,
OCT
HolmI. Integrated intensity^
measurements of vibration-
rotation bands of carbon
dioxide. II. Total ...
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18037Tlicsis T.Q-[_..
H69 I, Integrated intensitymeasurements for vibration-ro-
tation bands of carbon dioxide
.
II. Total absorptivity measure
ments on carbon dioxide at rocn
temperature.
Libraiy
U. S. Naval Post^paduate School
Mouterey, California
thesH69
I. Integrated intensity measurements for
3 2768 002 06927DUDLEY KNOX LIBRARY
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