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.

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