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-ERVICES TECINICAL Ifo ýAI.TION TiNCYAhRUNGMhN HALL T'ART PTr"T" .7.' i 0
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riKJ'ri(: whea goveront or other dravings, speci-rications or other data are uoed for any purposeother thbtn in connection vith a definitelv relatedgove=nent procuximent operation, the U. 8.Gove. ment thereby incurs no responsibility, nor anyobligation ehatsoeyer; anzd the fact t•Lt the Govern-mant may hwve formuat,4, fu-.hed•, or in any wy
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Research Report
:,: 'rared Absorption by Carbon Dioxide, Wattr Vapor,
and Minor Atmospheric Constituents
""cJ;OCOPY
PW;, C 1 0 -1; t0 W !J I"Yt, I ", _1
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Research Report
Infrarded AbsorpL.in by Carbon Dioxide, Water Vapor,atid Minor Atmospheric Constituents
DARRELL E. BURCH, DAVID GRYVNAK,EDGAR B. SINGLETON, WILBUR L FRANCE,
AND DUDLEY WIULAMS01H10 SIATF UNIVERSITY
CONTRACT AF 19(604)-2631
OPT!CAL FHY5K !.QORAlrOaY PW() ,
MN ~I WS'!(.~t *.!a--I AS( 'i~SfS goC C A&O Re P~t%~*qL Fj T'~ ' ~tI
PR v -": a-:
In 19:'. "A.L, publishd Geo.ihysieal Res.:arch Papers No. 10, t0:
uJbiul h.- ; av-ilahl, to a •ider audiknce. This report consained the r-aultsIh:,.. N. nnf. F. Burch. and D. Williams at tMe O•iao State Universi'.:,of t':eir studies on ;ong path kngth infrared absorption of water vapor Md Cari•c•diloxide. This report was almort :. unique source for this type of data and wafan i till is iilr,.At demand.
SIortly after ilt.it time Dr. Howard left the Ohio State group. but D,-. urchand others continued these infrared studiet. extend!ng them to other atmoaphericconstituents such :as N1Ct. CI14.-rd (O arsi to smaller concentratilons lowerpresur,, conditionb ricre appropriate to higher altitudes. In addition part of theabove %tcrk was r(-peatcd with ,cttler epectral resolution. The redult. of thiswork under contract AF19(604)-2633 with the Ohio State .rniversity were brol1 ghtistit i. til''"re.tr-- ' reports- AFWCiL-TiN-6;0-674, AFCRL 255. ajmd AFCRL 412.The den-3nd for these repnrts has exhltusted the supply. They are now beingpublisht-1 aS a 4ing,e papor in th, %FCRL Research Report seri. a for wider dis-
it1
ABSTRTJACT
irifi &red radiation t~v varin~as at mnonherii- vaqm It plareei under nnP env.er
three previously pullishe'I crciat actcr reports on 1) absorptfnn by natraus orlie.
tu.- -notioxidd. and methane; (2) absurplion by carbumn dioxide. and (3) absorp-
tic by %ater vapor mud n~itrous oxide.
kh iiPt - 1- M.J a fo -,I% t
PART A
by
IxrreU R..Vu~rch and Dudley WWIamu
A-$
EN I',,- It i I
I!. TmoRy
A. :sliMUTAN Lm5
B. ADGOIUJ'?X1 flA3DC
A. SMTROGRAP3, AIS 1WM CC=,.AND GAB-LQIDLII IQUIFPUT 1.%
B. WAStVMM Of TOTAL AUCSPTYO
C. UJIO& AND A(c.URCf
D. UV15S 20
V. EmRDIUM L MSUL MRO"
A. AUOS~OMI CIMY 816
i.'TAL ARIsOS1' AS A IMMOR
B.W~WAU1W 3'iuinyI
0. FW!!VIAR mqA2= LIN IS aB8P
AMI'RM~ON At P-06U. Alf P-OW. 3
A-tit
CONI t;NTS (CONT'D)-PAwR A
V7- V3 IWA,#MkuýAL AMS flU OYUT SMS or
A. MW 2143 eW1 CO 3&Me 6
VII. MM 3Wg, 1306, AMS 1ý5 m1 Cxqý MM 9
DI3LJOQhfl II
APT==z 1. &DORMcONz Byc
A-lw
LIST 01- TABLL3-PART Ai
Aiaoqbwvio Gs~es its3 btd fdr t*&M OkCU4 %.3 land U7
Dat h for h.w2143 WL o seat2
6 Data ?ter +%o 'Wv.-A.
7 &ANmry Of bolrIC3 CMA teate
LIST OF FI6GJRLS-PAWJ A.
ITwo views ath lpar.kI.-; ývipectrre--tr %Ith dual lat-pa s~WAt gA-handling #yet**.
Design of ob~t absorpum ctlia. 1
MAe "lftbtov~saia coefft--anz b for Its2224. corl 5~O baM. 9
hL Bpectra o! the z~ %ai' dkf
O~mom of ttz' ~
7 pe.t~ra of %be W2A rC3 V) b@M
d0 Opectra of the Mk crlJ No bhjvý
9. Cpucsca of the 222 am' 1 Ap ud
12 epee tm.. ahortw a~m ofl ther -- m"'
11 ~ ~ h V.Mt.1s.&.g7a of the 221 W1 - MA
12 MW~. ta~tai abeorptio ortb ZW4 cmi120 btmd sWesus heabW"= ;4,"wsm I'=t
soft1. encat-v 1 .
13JmftIr- rfe2"c-
1 Two viewr'. of uL- Farkin-Pishar bn~aeI
Oe.Ign of *hurt abaorptJicw celia. 17
fet.la- of the =%cl=. M
9t GOCtf Off*22-lS ad
0 spectr of the no to-, 3,,9 hem
u Vemtcrs of tbs 222h mtl1 X-O tcnC3
12 fte tawu "ay~ut~s of tthe GlbUM4 'qCSd Niwu *Vla2t ;ZOUUM for
saw1amis hevtlq afstwunt, val or eb-
Wim,% ^bwmeipttm oras? c-:1, q-.- vc.. Aeeulput t pof wW t9
mebigi u~e. "alr of &a~uetietfa re. ft~± '
fth-- Ut. t""I ubopm of V.0 ;E4awIme0 UM ""ONu "ehe~ie "a~st**a.
I :.7.01t 1 IGUI~ti's c-J):4 Fr
NIWO rid 'IKu' :Y,'
17 LI it percent abwurptioz. at &" l ver w
*~~~"-~ onP0t ~A ceM traSVA&i nI
zqulvalent preamurr Pir riwplasu v"re! ltmee
-.j the eutlmlen: pr--urzva.
19 The percent uasurptjLvn at 2V.O4 tcu VersUs
30Te r---:-t nto.-rptican a*. 221 o:-eeut~vltnt precauree f-;.: :izp~es nfiavar.: values of absorber concentration.
?1.me percent absorption at 2215r 1, zw in.u
I equivaient pnnusure for eamules whose vtLwts*of absorber eohwentratlon are proprntio-Al.
iTh ye rvont absorptio~n at f213 eel vre't-
8peetxt J1 Ut 214io 1 co- 7 oats. 6
I4 Lopenra v! the. 21-6 em4 CO brad. 6
S,:aof the 21).3 Cu1 eO bond.
I2t, Spectus tsC the 21"63 cr 1 CO band. 6
Usps-.:trn o: %to ;-i"65 call CO band. 6
C L*Iert- or tnee t'.- cor!4 - %%Mea.
Zu' flSpvctkr of the. V435 - 1 'OM band. 6
17? It.tal uml-s'Iflitc'n f tV :: z- L' Ca bwan.arnnm equidvilent prw¶9~wr4 for nap3e hav-
ing zocatant. vMqlaes of atbsorbereonttn.. A
he tvtaz 't.iUptn a -:- CA cr-'Atn 4 wirsý x rqitvtlev press im- rn- ese-toasvaitafi ro~ueu ef 6uisbrber 4C* tham
Ttil.ata-.r~t-r :f ttie Z143 g-xl Mland vezius abaA,.'er coneentnaUcs..
'..x !r~tal ebforptLlon of tte 2.4,0" *ICban~d versus wPr'"'2 .
thntrAl ahnnrptlion of the 2145 eas- CO
VIThe percent absnrptlcr. Pr .4618 cr 1I versusequivalent preessre.
The per-ceat. absorption at 2±&. rLVerSUS'Ire. 6II
The percent abborpion at 2116i -:&1' v-'w;;equivalent preuuiure. E
The pet cent atu'rption at. !L16 car versus
59 Frectrt of Lre u;Ž60 ,a- C4j tend.t6
.4!)Sp-!-:trnt Ate XO la!nd-. 86
".1 The cz t absorption of the M.'60 crt- %>4tealt versus equivalent prossure. 8
Z.9 LuiC .tttýrj;.Lta zr %UL 4Z63 W:a CaLand vertwn absorber concentratio. 3
-. #;tno t-he ITVs' .. u.- C1. kA..
.4. 4-pec*. 3? the 5ZC.. cr 1 CRz band.9
:1-1 ~ A -ýr the "OCC :r' c;e tatI.
SSpectra, o! '*e02 cr t C'4. I.!
£4- 8pectru ifI .t@ .tA es' .Ausa.
CA 'AM a
1.1%T 01I -T(,tF(I. (t1-16'1,,-'itIT A
Spectra rf ".r.e !'cm arn 1550 ca-lC11j, bands.
S•OGpectre of the -a5('L.2- and 1550 ""
CHI, ýtLndn *
Ctt banfo. .
7ue "utaLl ab•.u iwiuu vA' the '109C ca- 1 Cu.oand versus e j"u,.aent pressure.
5) The tot&,, abz-•rpti•n of the 3C.0 ca- JC1,band versus aobo..rtr -nncentrStlon. 106
5 The total absorption of the 1306 c"l Clhband versus equivalent pressure. 105
55 The total absorption of the 1306 i- CRM
band versus absoroer concentzMtlon. 1(0
56 The total absorption of the 15c0 earl CRi
57 The total absorpt~on of the 3W0 cmI1 Ck-band veizus vPeU.v. 110
58 The total aboori tln of the 1306 cz"1 CH4band vereum. VPeU. v/
APSORtPI 10'N 138\%T0 :;1j ()i 'HIDL C 'AMON XIONOXIM.
I. INTHODUTYTION
A detailed knc'vled- cf I nfra'-en tranerniqs!-rn of r:An#t.r výtra
pher- 1A rrl mA, ph~ný! in ",rneitiý,n* ý .ti~
"keat balar'ces and vith ý,he pos~ible develoier'n- of' in.-ared protinS anidgnaling isyntemz. During the past three-quar-ters of a century numarousdies of infrared transmission of tht ea&ýils atnoole.hre have been mand".
Molecular absorption in the atmosphere n. o&cneed :hiefly by Vater vapor,carbon azo~ae, =~d ozon-,--, .- ,c prerncco r v=L quan-.:ies or iruoxide, o:s-thoa monoxide, and methane also results in significant absorp.-tion; molecular oxygen alAc hae- absorption bands in the very near infrare-1.Infrared r-td1mcTn at±: Zf L,; Z-- -'
smoke in. 'h- thier t y.r-- -, a... w'ell!i
quantitative latak on. true molec:ular abto~rptlor field studies. Zen-e,laborato~ry stwirllpq of "evtfle*'- ý i-o- -y!-'1 eeen in~tulluric at.moapherrc work. an,! provide's;r u method of investirating%aborption in the ektmosphe:,n of o:.er planets.
The absorption of nwar infrared radiation ty at~osp~e-c Vases resuJltechiefly frum tran.-.lttas betveen the rotation-vribration enerKY levels ofmole~uies: absorlption In U.e. for- Infrer-1 !st rirouced by tranuitions he-tveen rorationa'. leveja. The ciluerved' trariemission by tlean samples oratnoaspheric gaee., iq therefj)re a fwnction cf tr~equeany v. If 1~,(v) repre-senta the intenzi sy of a weam ot ineidenL radiaticn as measured by a mono-chr~omtor set for frequency v it the vicinity of an abeorption bwsd, I,'ts feiind that the Interneity I~v.' of the redietion after ,Rzsage thr'ouga sample consistlIng of a mixture of VptO5 1o less5 ".au T0 v ba ratio
T()- I(,)/IO(v) is called the measured traawsnIsen'" of the pem sampleat f'r~qL~niy v and is exp'-uized e~ther s' cT onor a per-.entaxe.fte measured fractional absorption at frequency v Is #%.wvn by A~v) - -IT(v); A(v) wy also he Pst.%tA
4 an R ror-.n
tAge. It is found that themeasured %b-rlrtticn Aev iepe-4 on Aki~h rto:- as the total number ofabsori..ng molecules pet cross-sectiorial ar*a of the boam, dootod by !and ec~e'd *.knq absorber corv'entratior. or optic~al. density; the p-0
a eu"rk ur tLhe absurbLi.m Sa,, uhe total pressure 1, which in; ludes--- Wlpressnir. "f ab&scrbine and -nonitsnrbin4j &Laos; the aAoolu'e
teapmrture T of the 'smrle; and tht effect ive sUtwldth of the mono-
:r 1948~ %aimn c.-A lti~~r.n of tii, d~prtz'w~nt began a 1aboroan,ystudy Of no~ abeorjpion of wetrr- vapor "n carbon dioxi-le saxr's' oou-taining various awuntun of inraboorbing asses. The gas samp' u.-* or..nc.losed 11n a multl~le- trove roa. ceil Xjivn# a maxiu~m path length ofseveral meter-; the tesperakturv, of the V6 ma!* coý"d be elovatod byalectrlcql beating cf the ton.ro call. -n 195 Uowarl, Bur~b, andVilIis..ns' (hereafter referrvd to as HN), also of this laboratory, on-teaned 0h4 Parier studies of vator vapur .iriu. zariw d 'd to lonWrToth !enALi4 'ý o-Cr u a Z2-am.vr *i .I*- ,ra aL;t)L cell.in vtkich abjoiption pethx a& igreat as 1-ýX --ý.crw 'culd be ott&!-e!. 74owork "eporte~d by KMW w* 4ent vit~h -a-ea.' . :can tewporaturv.
in ttmee earilri ztudits it vas Yeririe-ý týAt. although the zeask-c!Ef A v) :.'r it 4 rn *smple liad given :,ith length are st-ongly di.
V.'V Total. Absorption()
.! LiUowl~rti prvdea tne ý11V V.1 SIMI vL are cllo.*n tojn--Iude an etitimr absorpti-in bond; t~.e va~idity of t~his statement Is dIs-
In acm detAli by 1kV. The inte~r-ml (1) 1. zalled tb- totskjpv"ý-ypuof or tte ats5IrctI.fl band~ de~ilwd h: t-.hc l~tm- v, r;..i v A am
i'quenwy usut., u tixn.- authors , r--rted to tte intexreiki an toe eju.1wi~enl bana -.rid tn or! the absorption, slqre the sawe Int~e~rel.can be considerid as %F7y'n, to- sn equlealent. Iansf having coeiplete atisorption over a req,,n-v li nI'rval
-j A(v),hr
Ite ",'K 0: Coapawan acid +.{ove and DrF N vat diraztei t,:vsjd thei- ,.uirt~f, the totLe2. nr f 2.,oT'i. frarse1 ban.is of water
a-d za-,-" -1 w'!u ai. ntrogen as ru~ctoxon of absorber-on-c,%tmtlc~i v, partial ,.--9urv p2 if t"- abectrbiog #am, total preassre
Pand absolute tesiper-tire T. The luationa ralationaLtpe betvwsa totalabsorpltiorn. or..!*he parameters listed werts giv-n by tables, hy saultable,gmjr.ns, and 1,y em:le quatl-)n appl!.rable to certain restrictatd map~s
to...al aboSnrji-n fcr eauc; band.
The yrtseot researrL pl.aincltues. fu rther s:tuidis of aboorp--cen by va!4r vaper w4 raz-bon d(irlde v-!Z a.1 axt~laslon to *pectral re-
igJuL-- and to Mitatee of v, j, P, %uj T n-i, -'overted it earlier sttzdles,aMA (iil atoula. ,f th* tInf:reri aboeortpten yroducred by the minor ia-mea-*ter'. t sitet .cu .,. carbon tin.owl4e, and vathtan*. 411W
poyfcu the ;ettIoIr esccAb-4%: t- !zatlocat ratatienshlp
fro varicue regotne Of C!.Aro~te.-itlc atcryti"n. 7!. fizertlomal rela-tint, WILL, so ir. the VINA8Cte ryPOrt*, be Sjlwn ty WhL10, .- rphs, a.-AQc;.r!rm' rq.4atlo"n. 11t .~ thea Zze r~eeo.lts of Owe IniestIMOcVill prf.v* Uefo. in 'het UCr'vlrVng e
rV41:eilrtlr.t ýt a 6, u X.r LOv. qhzlý? teblVJw
(iitearidisionof~ atmoopberi7 :csoeltito b7
a.! .,n .% %,-- 2Acv i-:t o -e.Atb inf iy4
stmopL1m.; scd
(c) test of the vartcus t~acrles tbt2lsve 'amupro~t-i to Saccct fro abdorpt±oa pbfl mmu.
?-Le rvvu..ts cbtained In~ "A ;ylea.n rc..oProgram V- Do
la =&.**C..j. -,
vtrot Qvvrtoc .'2tC -s- band, asol~i$ne of meham-n-lea at :-,5 -a-'. Ind. 1,106 em--.
F3?MR 11; Absorj2-on by :artxi UoýM bands a,
at :Oý -- r: &ad inl ¶4* re~r.f s'. 'ý 0 .
F!SL. KMPORT: Ab.'orptll)c by w~atr apo.- to the -vidon 'i its wtbr~tFn-Mr~At~m )-mis at 154 -a-
an ar )'x cs-, a nd ta Uw vgomk af its pureanal3~ ban In the tSag. 00 - 100C at~o-,P
7.htim *f~'~e ~ Iz~~.rep pe am tb's
A p,'rtien of --ŽA WA~ !m -, SC, Xc. aM4 'c- ust vqwvrouttrvczyi-ý a u~ ~se*-taion er a c:' uoa. lowevr. addit1ou.1
,ýq .. si. As a rve.2 .. ! tb~es isij:a ts @A or thr e*irtc..
-S-9
11 'HECRY
-F'wtja ebArt u absorptionwhich ans proposed by latienrt ne.-rly h ~ungrce -.rejrs ago on the basisor studles of abduryLic_. of lighit by ,iquids, and was later eisboratedby Beer. Accorcting to the l~ambert 'law, -1e fractiona'. abso.-ption AI(v)for *orvy.,hromtic radI.,i~tozi cf frequency v iir given by the enreasion
A'(Y) k- 1 -
8 orbing catezial and v Im ýho- abcorber c,,n,,Lr'.~rat~on. Beer's elaborationof the law was (ýnoorr.. w'41h 2f cz!61o Ac ir-
to Beer's i~w
k IV'. Ce,s + Ct)+C %ek ... ()
where C1, C. are the concentration% of the Votrlýns ccs.nontz
fliients' for the various co~ipo5,.is !Fter5s 1AW is 14.-1 on th, r.!ILZp-tl±zr that each ubiorb~n.g , ole,:l absiurti' radilation Independentl~y .. ft,,,ery otheqr .wilecule.
Vairvi,-. ..- ly tvi Ier.:-t- miur tt lre Boesr i.Aw for infmrarsiSbvrt&o S&e Arr dti-uiuse b:, MW. Th* failure c bet Isa law
-anr 14 trazal two 60ources.
(11 in tbw f'irat plact. ArT- ML have riojte shsa nd *".-mrorv LlrrM 3wk~turaen'. ýf ^A( . If ijapuosit'u, niucetri'y a&jnoChro~t I. readision is r-ot heing Masured. In the-a:, of br)~d. r. q'*.ucuv 1-ise banil observed for
11qo!3s. the m*%-jarvia,1 r~t A~v) approa.hva A-(y); itwas~~~~~~ thi or../:i~r..' c A~ t) and A'( ) that led ý.j.&brt
ajd !"t r *o tbe forui-latian of their Loven. the Infrared spse-trua of a gas corelisto of bania emwvmA~d .'!,dvdl iwitm r~w~uItln~g r~pid '-Intlos of A'(v) wil.. r. vIItx 'TaeWvilmjia tbat a-y unetjally rsrmv~ %a ccsnpard withi the spectral
PV~a r~d_ t j a su-i*~chromnts- vr spectrograph set topass ladl.ti-n of frequency v, tkw meas-Ame At.) --a riot UMU^1IYa close *pprcox!mtlor. of A'(v'. Thu., I t In not surprisinuthat therv Is app*LrrnL Ni.lui" of the sIire- absorytion 'Awv(3) anid tii if !i a toest. wn-me Oc- rption A(ss) to "94t to7-:Z.;';i A' tv) tin ý,!;. -7.-, t)qse aple IA.& N.il ro:- O*)or. f2,~az..sutA' isacs:, tv-t when mome @oV"'nuit'a~PA evinpri-
a:rsn .honr) rrid C s-trw ci ame mis.
(ii) Am lncliceted above, Beer's law lIi based ..n thr aps'iup-tiou that, thw absorrtion o c-, :n molecule Is independq'~-.iji every otner P'tecu~c. -= is ISUaPTio is lot Xj'st.-fiec! for the :aee in which tk'e absorbing molei'1e. t.rpor-.ences collislons with other macIeculesi, mince tkolect.lnrcollisions res,1t in ape~reciable brordeniag of the spectrallines.
Rven in Wne case of noninteractin4 aulevul*@, spectral lines havefl..ito natural] widths rela7Led to the uucertainty principle which p~ro-
Eosan uncertainty £4I in nn enerdy 1lovel related to the lifetime At ofthe a leo'j.Le ui the level tv tile relatioan A-- .lfro all excltt~ri level~s, all spectral !'nee In.'olvizng transitions betweenground a tate. and excited otatos would be e--ected to have or uncertsi~ntfin fre juenicy 4w - WlLhzl/4t. !%atural1 broadening is independent ofefeCLI. external tj the zunleculr. Ususilly natural broeder~ing Is negli-gible ts comnpered with line brc@Atmnin due to t-'e Doppler cffect, whichis re t-ed to the tealwrature of the gat esapyle ajA produc.~a noticeableeffe: -; hen absorption of ugases at very low VreaeiLr*& is zv"%Lired,Di.opplez vr adeising is indepnit-t of preasure. Ile rostributiome ofnatural wilth: =:! Lc;;-le!- brcteical to ~.*it-a eltfhz of spectralV1xi*s are usivally negligible ao ozopa~red wt.th zontributiorta produced by'it@ larje electric fields that act. du~ring &o~e,-:Lar collisilons. The fre-f incy of sote-z'lar collislona _1z rclatcd to pressure and hence tL@ t','tai.1 wiý '1~s asuý related to pressure excep.t at. extremely low pressure,..
P-.1-i~ .f Lnae beyuu4 Q% !,Itu& &LtriiiutLale Wo LAt~ual wiiths &&Ith,ý t..oypltr qtffo-t is uesinlly referred t-o as "prrvsure brtadentag", oaterm which !nciudes off*,". attributabl, to collliiain tamping, to pressureshifts, and W Start, ef"- to hru4
t o.aLep.ahs tWv-'n
soleCiUe&$. The tpresez't v.-r' deals 'jrimsilly w~th stwdles of collisionb~ose ein, since the rto. * of prreasresa doe.i not extend to tsieeflorsolpresalurve required to yr,. .eymeettat..~to Stark ztifto, ud4 en-forced dipole effv-wts. Calliasii iwro*Ldetlt4 is usuai.~y tncuuitierod whe"tZhe tizW: tctV~cc :.lciz z 1noc ln-g: d W d.= tna tluz ~ulIcnUol_6t the other effects are -n~~vusikre4 whti~ time spent in collte1iosIs ls~zute and involves riadiatilon abeo~ted dur~ne cvlisions.
A. I Wh~ENTZIAN LINES~
Jtliough the okpoerimaW~ r-suIla ntle~z~l in ths praeast In ea&tig&-t. -1 ?Are 1It dependeni Muplo asb..JpLL.Jns 9s tic the GCtUV_ ... ePeS Of SPectral11.:es, it is convencient f-- purp'oe.a of 11&rsetuson to hasace a line shape'rat rroposed by Lorentt Lad toiand to gi~e a satinfactor-a alppfox~smititm
actuaLl line staccets uowr the fV-1f wide rage -.1 pracaures ini wblchollir!l.o damping" or 11.lon tr.re!ennz is *nccinta.red. "'i axpres-
cion 13r tAe ausurpLtA. ;:--... _j .......
Qr____
kiv-v) 4 *
vherr the, *ine atm. 4tb S alj ~ Io is st. - a'fVldth or tic .1
nirtor.-ade.ncd 1.Ofe 's 'I -,:sn :C- .to probbillitlez .:'t.-n~naions netween tr'e :rat~.a and final energyL-- -k ~oi nd z.Lo the .-e!.Ativ~e ;opulati..na of thbeselevels. The hal i-vidth C& is related to the pr-psure, tho absotule teuperietare, and the tv-ner -f molecules in the --s~ stmple.
Ladent~erg and Rei'-he1 4 have shownr ttiat vi'.h tne value of x(výs In )buost~uted In ( 5) the integ~ra2.
(A~;~~((IV
ca be eva,am.-l t -m-f -j ,.ni w prouitwe-j tae Anita ', A tMLion Inolladp the entire Atrcr~tion aac'elvritz. a given lire. Thus,on the assunytion ttut vi tl akrprla r .1L'.i 7,'iteg~ration.f A(v)4v m fA~v4K~v, It 15 FpIthlfl I 01Z.Alr. -- w!6n t*Pt..ýLaijii~erK ard flihe cic ::u~e. r -T ! 15.12t I.n~itats that
41b a a -t v'.-.ci
A~rt!iuj Eq. ýr) is a ii~ nveclw-1 expross1n, K~saase~r' h*
tl* atoor~tiov of' alnge~ Atrw ýnlr -7*.Ain UL~tnrW roCAW41t4:
v ~)4iv -Sv fe:r am'.I x 'wwak n'
a-re-f,&atm, 'irlrg ~rJL 1n~
As in~dicated earlier, the lino rt-Vagth S' (-f a cc11isioa-brc&!,-n~dline In a conmtaxg~t at a r;ver taimiarature. The absor'uer ce'fcentri~t an&-. aL gpvn tvauersture is carectly proportlona.L ýo .ae produ~ct 0,: t~ftpatrtial prosseur R and the s~~l~palb ienVth: v-91~. The rel~ationbmenui the b~lf-vidth and the preeeoare, tesqmratu.re, and com~oettion ofthe saimple t sim*wbhat sure involved.
Tb. hal.f-vidth a of a --oll~sion-brakdoed man.-1~m! 11wn* Is ~~*tIonal W.~ too colelson frequencyF. From k~inet.I theory it can be shavnthat the ball-width is tiven by the relation
w~r* k1I the nimster of solatulso of the i-th type per uait volino,Do i &smo Wi ~Vcep~c culi~air, diameters of the aboorting
sole: 4s and a mclecgule of the i-th type, k to Boltzmnnaos oamtaat, T1. Ihe aebcl~uto tmmomaýro, V* to the mass !)f the aboortlog =nieedi*,as* ft Is the uses of a miscL.e or tke 1-11 type.
16 V: o b.u. AAV.ua ft P COAem i ;1ii Ime dAeA§Uimm tur aaluas imiture Lf @Loe. !a V.th s the e -i~o t ths Peztiel Pmemare of#)w o.sgwr"et eve *he Po" f-r a! I valw of Thbe q~I'W ;Y,5*oU. to-calling that 'he pearUal preeaa, 1-f -.1 Ow-f the I-1A type 10 *pmaby p, St 3k? amA "asemi g Usthto ac Los m ice im'.,. ane ihedepeonoi of
~rtimDsmre, Om "a reaull ehcm that for a atuma odauys o at o-- theha.1.-wifth of avasic-b~an helte r bea he tt
V4rV Q0 16 tm Laijf-Vttth ofthe J&e =_V40 AMM& 40SaWOM r^dkta t,.29; at a gives t"Weravzr, the ýAlf-wluth a WWAU in Awated to ie
9.Woettltmou of tm %e - cf It gives t-y tkLI is val&Umw (8) OM(9) lfaM, to tbe fat-VIVA prroctioo. for a #-V mu.xet~!
A(v d -# -VP"r mU1 z 'We" U:4) (8
IA~v)~~v'SFT' -- U'p !&SI 8,~ a (etA4 lIie) (9')
S &Mple cunsie'tink of IS Sik. Lb U3Oýf -h V p.b 1no adxur f
,.e jAS, ý )iv iiw - SN :X- Y r. ?ralc line) r.~
Jý i.,r ýarge A czronz iirp)
U... s c. ita-%tr in vhi:h a r-1-rn ar-u-- if' messe Im stud.&d
nýo.r *-.:wparw t^ *'' ! o! A) -- ,,1,, tf2 ures of diff re at pl,%pcr-tioni of at:-ý T.A~i~' ~ -* ". -,f "r~ ..
sf~Aon spectrs. Linea. S±me. Mot ::ft- Ieps su*espe ouploy~a In.texperimnts. vora zonetst.aI if binary uixturts 311 cboorbin ag o*an-n"In-goz - .1 a. w%& 4**, as a ncvab*.jgbiag -vnw4.5IgI po', it Is
d~aormb1. ~o -,.AuaI: V)J !Or *.b* COSSia eeOf 6 b1VA-y DIAI.4r# Of&.3 ftb4V-VCWU 05 a FAMi b roacenas~a V.a !. I~e s~ __st .- ' 7 ,1In this 7&St hAV tvn -*rum; a self-broadendag tomU !n vb.Ic I - a, W
ase.:ca1 tam~ for th* *ff!ets of b-v*Aea!iF~ by tA* tnrt psa I - tLuautl~ %iasos .tLm rL ru
* -~k] (LaJ.~1 b1
wu s~a. 'Nf aIboatlt~ &ad b~4*.4~ News. Nt 1%4 t~tat. Use WVIOOA P p- 1% # ps *c ft. % tT ' - e f~ C %o tr%. ef p
aA wy t-wrLL.ii4 i )i Lbe fk ot
whorer B3 ir Iculled the neii-cioaleninm cottricient or the ab-
tbe absorbing gas to t..P "brcoadonisu4 rtbIlIty' rot Use nor~ba.;Db!- L'.
where P it flle MeMSUreJ LOWA I preasure of tne sampl~e and p Is Lb. Partialýrauecf the sasorbi.ng gnL. iThe predictions ezbodied in (e8) and
j9') ahoula De ruxirileal -, u a~x.ure of Pnses provided F in replacedby a rrnrI1^t. .. iivRk~oa.rt rr.--.r. P T- .1..0 1- 4 - - -
theory presented th-ur f.~r be-i t-c cpeved to ap~ply to 11=Ps vh.'e vldtisIsa dcte mined -!% r~' I-,!-r:ý 1!ý I = 1,cnn~ 1.t 1i r. t appllcae,1e z --ertranalyi: ±w prea.a.ure.-, for which nnttural, width3 and Doppler b'neafnIngare ot primary impnrtA~nce, n~.r to oxtremel:' high pressure., at whicaaboorption during collsilons or "close approeches" leads W Str effertsand asymmetrical pressure vhbIt.s-
B. AJISORPI'ON BAME
Tfl nr~er ttw extendi t-o theory to Include WtAal absorption of entirebar~di It is nreisptrj to consider tne spacing@ and inatenasities i~f the
more than one huae uonI-nbuts to the absorption at. frequneny Y, A'(w)in ks.'li giv*en "I- itq .f the value of k(v) used Is the am of thea~v) j.or eat-h cf t~Ir.-v~iaft. lines. EquaLIof (6) also Yields thetotal abscrptior. !:, Fin t-nt!!v band 1jg the proper v"lue o? k(V) is us".For the simpl- *ýve (of n-) jverItt;p~ng of the 1inen, the total. atborptJonof a bund ru-:- ic trLa..' ;&z t. io.z.. .1 f L~r L.LL .aeiLivub u* vai vZ
the linez.
In ord¶er tec =-,:e the-ore,!ca... icslcu3.Ations at the dependi'aee of tot&:.absý..jiLion of an entire bar.i on~ preavure and absorber concentration, itIs usuaily necessary to make sawm aosumpt!uns about the spactuaaf sendnt&. ,dta.#- 4of Ojw In-lv1,usl 1f.a.' N.'iffem-nt ideaiI&Ad 'um models
bave received gew'le :ra~cogpdti,)n:
(a j A bamd *!o'"71cting o.f an Inf±'vitte array of eq~u~hlyinteon5r, 'ewi-lly npa:eed lines hp- been treated by
0 A dtasjr,1.rr NiaM, utually referred to as t'he
¶-"nu~tIt.. %:-i Wc reproinen'.ed by a probability'
1' ..j t n" toy 1~ 1h."
'~th± I
- J -l._W.bjae: -rouet wnOLO Ir comrrcoed
csocera' rjL:- .AesR02 of' vMOCý tn-d'-*vII-,aII' I,.nnm, ziKsaj- band, Lut where-coese groups are -zyerpz-.sed to giv,! a nearly
- 3s pacing.
Th-a rport by Piass. also includes cur-ves which relate absorption tosbcct ~cr nnentrett s and pressure Car the f!,-Pr lt!!ereat band moilels.
- ~ ~ ~ i 7-t. re U rrr thazt at
.,afldn can be explained by 1Thc ELasaeer model*. it .,a: alsu demonstrated
=:deI r- It in r.-V. --tjcrfl or -I---' by C0e iha t1
a:es best ed above.bac arproximatrLand perits the cabsorption to e inexprtesse in term -.soelemnt sary unas ond thins val gdj over ab uasideabl rane oftepsitesuand sabsorbe ontenItration.z varys almost atprandtonm avre (i)T andthe
lineapzrrdstion;a(ti vxpeablcs4 ppin fft lastorptiand oifi even-.the4ldueg ,ý -promjuoe. athre coiT.Le flT aoevre vlalid h~asrdiccsWetthsrec1 rp n-t the spetnr linus nofrap and, mtho. (iii nl va lislids-tetherborenot he absrorpmtion lerines the eabsorpetion t eepese.ntrao
elmntariy ruccrplctndi v1 rtali nvear th uverierrl ofatge st rong- xes ieand abobrc entaincrTease ineth-erapprorximaresuls arn (in- SMcresede beorptlonti in the' ira'ng4ar of Ethehesonly.n T(iii rooefl-
Ing gLYniw ierE. (9 an c-'--ponrd todl. ofvg vales& wan
li nes the setutu .ttczrpttc of, an banhd (111 1e trated aswhethrosut otthhtta absorptionsln- -wa of al ot te itsuad o
sitrongline the sotal absvorptio:n ofa the ban ishsep fistoqs. (9),s (13) and (114)as to beit vroortiona tolt (-in)in-
cre ansed Asof vties on th a~nd ovf hc thi-lns rela.tinship-
isml value s referr.tora the- sqare-rof ot vreonp. Wf henlines lJthent uttroeolnsr thedtotal.be treatied noil
s±on~r thetotal absrtosiof ae sur-'ot dhe endne; hodever, h
sT' eittrong of is the h;a as-orptio ofther blndi seaf
the eqialgen profvales epoyead Pe. ovrum:. hs eaiosl
itý vlil i refrrcd o-&, ithesur- trgo.We
The &lia.ttnguisa' g feature of the atrong line aprozLmazionif *tV ' the total istsorot5cn cua be zxpressed an a Puli-tion
Wtesinge TlabJle vk . The distinction bLatieeo tesquare-root depen-ence encountered for strong *3n-over-lapping lines and the more general strong-line approxims-tion with referenae to entire bar.? is emphasized; toesquare-root dependence can be considered as a special --asoof the strona-line 3uprximLution, and tot 11 only Ahenthe spectral lines do not overlap appreciably.
(ii) The weak-line approx4matlon is valid wben ithe absn"'tion is small at all frequenries in Lhe band, includingLhouse near the centeriR n tte Z' rQ:ge~t jbortfonlis..M,. requiremeut ft~r the validity of them weak ~line upproximk-tion with reference to au entire band is similar to the ro-quirewent for the vesak-21ine apprcd.rt~cn for A rng2.e linegiven in Eq. (8). Wei requirement Is satisfied in the caseof small valuee of v and large values of th, 2e totalabsorption of a given band Is a function al v ; however,the simpl!- linear relationship given by R1. aPi not validiA the C~aze Ur U'wr-ilapping.
(iii) jae non-overlappi g approximation is valid when the.eiq not apyreciabýe overiapping or the lines; and the total
=;Upt ýic 1zgir b- '-. (') wIth the evuUL-buLion of allthe Individ~ial lines ad-iot together.
It In possible to teet the usefulness of a xiven band model by cow-paring the results of total absorptle n measurements with the theoreticalpredi.:tlona for ranges of values of v and Pe over which the strong-lineapproximation is exyjcted' to be vai.The rtrong-line apprortmtionis useful for testing different band model,, sines the total aboorptiondepsads on the dic~.ribution of the strenet.hpt rf fha 14"oem a-- wal
uj''n ;%ýZ-14emntof tile cr:P t~z_. -nes, are. I; 4=8t dirferent for414 ffereent ,.o..A modelC Emcwavnr, the weak. lrma 6apjjrwsImmLiun and the
non-nerlpingapproxisition cannot be used to test diff&eint bnmodels since th-e total absorption is vr-wall:~ lalependent, of the Ua&~7-i-Fi74 mnd ---a '_st;'but~ou if Lije s;rengU3s of the lines.
Of the gaes treated in the present report, 0O and N2 0 are linearmolecules whose absorpllon banwbs are couposeed of lines having gre~allaUychangiug intensity .ond spacing. The btructure of thece bands is bestapproximated by an Elzaaser modelr: and f,; is therefore useful to cnwprethe N2 0 and CO data In the present study with results based on the31aseser theoretical model for values of v anhd Pe for which the strong..line approximation would be expected to be- Yalid.
It will be showi below i:) the diricussion of each of the bands In-volveo. thit the Elsasser model is suf:Licient. to predict, in a generalvay, the de.e-.dence of to.tal abs.~rption on. absorber con..ontration asd
12.
pressure. However, it will be seen that the ererimenta2ly observedeffect o? increisin� pressur is �ignifican�'' 2.ees than that ptedIctc�:
�u �bber7 u�au ±.j: certein YSJU2S 01 V �r1a re.
C. SAUD IW�I�S
One quantity of fundamental importance in * tudies of molecularspcctra is a quantity called band strer.gth or �nd � Jk(v)dv.a quantity analogous to the line ctrength deftoed in Connection with (5)c-e..t for the fact that the limits of integration are chosen to �i2Ciudsnc entire hani. It fk(v)dy �e l�nowe for a vibration-rotation bend, basic±n.iumLi�ju cuncerniog Lransition ments appropriate to tvinaitions be-tween �l�.,rat�onal levels can be obtained; the value of fk(v)dv also de-pends upon the population differences between t�e lover and. upper levelsand ja ti�cef.yre nien e fiI'v't�c.b, ,t temperatu?�.
?�r� the data on total abrorpt�"" to be presented later in there-port, it is scuetimes possible to determine a value of band intensityfor the various bands to be investigated. This quantity Can be evnl.uatedfc�n total abi�rpti�ii 5ea ie�i�t� jn v1]eil �.(v)w« 2. £o� all frequ.nciosincluded in absorotton. Under tois condition, an integral similar to(6) but vith the l±aits of integration chosen 1�o include an entire bandbec-.
JA(v)dv - vjk(�.)dv (6)
for �c'v)v« 1 tbrou�bout the e-vc±re band. Since fA(v)de and w can bothhe measured, the band inten.�ityfk(l')dv can be determined. The choiceo t absorber concentrations and proreure for -ihlCh (6') applies viii bediscursod lacer in sone detail.
A, PC2.CiPS ATRSOFRp'1J Czi.LS,
in Lhe PrEcant Stu'J', a X_'uble -beam, sing~c-pass Perlin-Elawr JtidelZ! spectr ter vita N&C! prisr.i w;_- -,loytd. for rre:1tence-s betv-aen40DOO cm-1 and 670 ca-1. This spectrograph vas equipped vith a dri-o
a--':-Zý~rdc k."l'i- a UICL Plut cf A(T) Ts. V On 1j,e-jorder chart. In Pie. Iare shownm to vievs of the NodP1 21. -4th duallong-path cells desismed anti -nmr-!te-2 specifically fo-r 'it by Perkia-Kiser. in tn-ti pper par-t )f the figure the sample ceL.. housing has beenrenoued to show the ukitiple- reflection system which utilizes the Whitel')principle. The two cells, which extend from either MU i nf the Qw+'..ý6to;A'*, P inent!'i ý_- a .- emgd:;ta.t-y may be usail aliul~aurm"uy,cne in the sample beem and one in the reference been. In the lov1er partof the figure the sample cell housing is shows In Dlace; the cell. lous-Ing Is designed to hold vacuum and gauge prennores up to 100 pounds persquare_ Inch. A portable gas-bandling system' which vas constructed for.Žjue prvie-est investization is snown in both ,T1"_ MAn lo d~scu!!sed bellov.
Each call has a base path of =ne meter, and can be adjustec'. to 4tran-csa1z -ý-a~ ..aalli numnber tiiviuioie P'j rotu. The rell housing-' t be- la~ order to adýu L~ic nmr'er of zraverWRa.L Althoughelcotriceal heating coils around the cell bousih, are capable of 'Masting,the cells to evplroziuantely 1000C, the data included in the preitnt rtudywere ýbtaine4 with the samples near 300C.
Very little effor. is inv;Olve-d! In- ova..ing from the dual long-pathcelis ~to conventional 5kvort. eajppe cells, or 'vice 'versa. In oruer touse the long-path cells a set of kineamtically mounted optics fits intothe samplIng space bptw.een the "Iell and directs the readiation Into thenel=1 n f:r= thezdl t. ML. u. Tete optles, vnIcli arenot vIsib:e in Fig. 1, cw. be easily removed when sb-crt cells are to 1wused.
The mini Woay oz ~no gas-naw"ndig sys em shown 3n ?1g. I Lad a1'Bothe packless minsiatue vftives ware sede of A1.131 ~6 stainless stus.- YUhiowould withstandl high pressures and twould also allow tiw woesible futureuse uLr ma gases which are cor%.'.lve to carbon steel end tionrerounsmetals. One cf six outlet valves was zoninscted to the aemle 'ý*l, oneto the reference cell, and any of the cther four coull 'ae coraucteat tocylinders of ecs beiag =sed. fte pressure In tWe ostaim was recordadby one of four different Saugea desil.'e4 for diff-erent preisure ranger.A Wallace and I4ornmn skhginlvite "re--.re pug, vac"uwed -'r the pressulerange oetween 1. and 5n0e HRi. This gauejj In calibrared free 0 tu 50
Hm g and is designed to ..&vv &an wacuracy n±f cu part in )u prnri'wdthe "zesro" is properly etdjusted. A Nclar-! gauge vas used fo; absoluteproessures less than 1.5 SO Hg and also seived as a check of the rendings
13
Fig. I. 'No vieve of Vie' Per.tin-KE.nwr Mi.""-, Sp-i ttronmcteruIth doot. long-path cells ard
ofi the Wallnuv andl zier-wn gaug~e ut. low pressures. A simple "IV'-tuoemauometer served tc measure pressuler. it the rnrnge from 50 E. Ticone atmosphere. An Aeh~roft 'fl ragauge', whlich is a Bourdon uepressure pAuge, was used in th,, hdiger pressure range.* The' Asbcruýftgauge Is also constructed from AIST 511 stain less steel er.d is calibrateidfor gauge piessures between 0 and 100 pouads per squaxe inch in stepsof one pourid per square inch.
Before intruoucing a sample into the sample ce.1l, tht. entire gr.s-handling system vas evacualed, -;he reference cell was ClO.3ed off, aridthe nbsorbing gas was added to -Iie syst~em Pnd to the smp~le cell at thedesired pressure. The vallve to the sample cell was then closed. Inýzder to produ-e a sample with the same absorber coneentratlor butgreater total pressure; nitrogen was added To mne samp Le. iielore rlie
rltr~v -iintroduced, tl~e ga!:-harirdlin- -ytem (excluding the samplecell) was evat'uated in order to prevent more absorber frw~ beina forcedinto the cell. !Mitroger, -.as hen added to the csyftem to L. piessueeSlightly greater than that in the cell before the valve %as opened; morealtr.'gea was then added to the sample cell. unti~l the desired pressurewas reached. This procedure vwa followed in order to relucrt the flovof absorber from the cell back into the rest of the system. To produceat !ttple of still nieh.- totsl sm ,mnre nitroFP~en wes added to thesystem, without evacuating it; the valve Ietween the mair. 3ystem and thesample cell was then opened anW nitrogen added to the desired pressure.This procedure could be repeated sotveral times to measure the tntalabouryLiust r ra surleu. uf esamples having the namsm absorber conrientratjionand varying total pressure.
lit order to reduce tbe n'han~c, of the ar'sorber diffusing f:'rof theasaple cell back througb lbs valve, the valve was kspt open for theminimumt tims required wo allow the pressure to cone to ezqulIttrium. Itts probabie that most o,* the absorto- which did in some way get out ofthe cell would remin for several minutes in the ';-foot length of avalltubing which connaected tlb" zel to tlie rest uf the &ystem. When morenitrOgen VMS sOidd woet o!' thts #absrber wo-LW t~s vo.~cod Ulca into thecell, and sany losses of this type would not be civemlative. It vwa foundthe' tVe observe& absorption of a sample of -ov riborber partial presoturewith nitrogen added to a high preseuvir in om step agree, -.oil withasim~ilar u....ple ina whicna the Lu trogrm was a-ided ov severai suceresi vesteps, thus indicating that leskage of bce abinrebr through the valnrwas aegligible.
When samples containing two grzen vere being studied, It vas *a-sentisa. that the Venes tK, Uhoroughly mixed to ensure thet the pno'eramout of absorber was contained In the radiation peth. One adght a'x-poct that ea nitrogen vex being added to a sample, the absorber wouldtend to move to the part of the '.1.1 avty from the entrance; and, untilthe pss@ become uniformly mixed, by therma motlion or otherwise, afalse aboorwtion reading would be obtairn"t. It. ,s amasiid that rýu.iform gas mixure had be...4 d nhlbin wo' _1A -;to of the sample had
1s
reached a constant velut,. The aixIng problem was Investigate4 for eachiof the different absorp-cion celln: uoet.
A fan nas Deen DUllit in the rrrxin-czaer iong-patn ceCiIs to speeatp mixiag. Wlt1vuL Lhe fan sc'.-,a ai1Ae6 aie iequired fur aixLug ofsamples at high pressures; however, only a few seconds are required for=ixign when the fan is used. The fan blade is connected to a shaft whichextends through a rotatlin vacuum seal to a syall electric mutor outsikethe cell. The motor, which is mounted above the sample cell, can beseen in the lover portion of Fig. 1 The necessity for forced mixingprobUbly arises from the fact that the cantilever, which boidJ one oftl-e mirro; ianside the cell and is visible in the upper portion of Fig. 1
to the otner apparentLy occurs ratner sowvi.y.
Figure 2 is a drnwiag vt-ý' oftvshort cells which were used, one 1.55 cm and Ubý OtIer -. 35 -w lung.Thne zynthetic buna-N '0" ring between the w- ndow and the cell body servesas the seal, and the windows are held in place by brass end plates joinedby threaded brn rodR. The grooves for the "0' rings are not deepenougm to aUoliet.- to-vlrd.: reta.; this reduces any local asressescaused by irregularities in the windows or metal which might tend tocrack the window-. An '0" ring, between the end place and window servesas a cushil;r &ad "1z; L= th"0" 1'.u) deftl. Main melon ipninnible tc bohi the -- ,iAows on c i i;ly .,1hvuu producing appreciableshearing stress. The short ce 1 can be used for vacuum and for gugepressures u9 to 60 pslg. urooves were, fi ied in one endplate which fitsinto a rceptacle provided on the spectmmeter directly in front of theentrance slit. Two NaCl windvc! were put in the reference beam to correctfor the attenuation by the cell windows.
Tt wvs found that. miv-ng wns fesnti.illy r'om]plete in the short naf towithin a fvy icconda. HIowever, a few mlnute, were required for mi.txngk.. i somewhat similar cell -t :>vc-l fu the 1huWo i Fig. 2 inthat the valve was Joined +.o th, mair body of the cell by approximatelytwS lncb-• ,f tubing. The vaiwv was cobdered directly to the cells ausdin Lhe later work. It is probable that the rather long mixing time forthe first type of neil was csuseq by the fact that =VufTion throughthe small-bore tubing to the val,- rook place very slowly.
Studies of the 4260 =-l. 'Cm bnLd we-, =de with a P.-kin-E2mar Z&4.l99 6pesdrouiter with a LIF prism. A Wernat glover aeevcd as a radiationsource and a thermocouple was uoed as the detector. The sigal wva as-plified by a Prktn-Elmer Model ]T aip~fter and the spectrum dlspl Aya~by a Leeds end Northrup Speedomax 1 'd".,r. A mu.1tiple-pawe tell witha White!0 )pticvil 1yem and external adJuatmtnte was used with theModal V, apectromtei. The base length of the cell is 1.5 meter* andpaths as long as 4L meteri were .ed, alothough paths twice this greatcan be obtaine4 Thi""l ,y uf thp c'll is Steei, the end plates alumit,c,and the vindows NaC. Total preseures are limitted to atmosphcrVc and less.
L Ji m R o d
Fig. 2. Decigzn of' uhom ab~orption cells
Absorption Iu• nýtnt. wiLa the h.1Tjuise.-na&s COI! uns4 in thestuy of the 4260 na-i CO band indicate that mirxing is complete wiWdnseweral seconds after nitrng.is ' ntroduced; therefore, forced alxln-us not necessaiy.
B. S"U•R•.JT OF TCTAL ADSORPTION
ite total absorptioc of the samples studied with the Model 21 spec-trometer was easily determined by measuring the area under each recordedspectrtm with a compensating polar plaaimeter. The abscissa was linearin Irequsnoy v and the ordinate vas linear in fructional absorptiou A(y);theireftre the area tinder the absorptjr'n curve ums proportional to thetwtal absorption. In some cases slight corrections had to be made forenattered light and for differences I-- deflection corresponding to zero"bsorptinn. Such differences were caused by t,,t-iql Rttenntion insample n.d reference bcn-- ty t 1 sn;tYUw6" d b:: the atzospneri j euwithin the iastrument. These effect. were easily corrected so that negli-gible error in the measurement of total absorption vas caused by them.
Spectra of the 4260 can' band obtair-, with the •odel 99 spectroe-eter t'crc replotted beforn being measured. An "envelope' spectrw wasobtained with the cell evacuated, "&d was superimposed on each samplespectrum. The envelope spectrm served as the Porn po-a . _curve ari the spectrum was replotted on a scale whose ordinate vaslneu, in n"t. ; o---loo. ibe area under the repiorted curve
was then measuted and multiplied by an appropriate "norie!-34ing f-itor"to determine the total absorption. This prucess of replotting the spectrahas been discussed in detail by gOW2.
C. IRROM AND ACCURACY
The possible sources of error in a study nich as this my he d•.idedInto three categories:
(1) errors in sampling of the gases (in determin-Ing the amount of absorbing ps and nitrogenin the cell),
(i) errors arising from inaccurate recording by4te sp-,tr•leter due to roloe, drift., sod non-
linearity in the detection.snpiiflcation-re-cording syntem;
Ciii) errors in measuring the recorded spectra.
1. Smling Errors
The major sjurce oi error ir. canp.zl is the cfft(ct c(' L!-ýcr-)tiln of the gases on th- cell walls; the problems involved are discusser;in great detail in Appendix I. Another source of samplizg error involvesthe accuracy with which the pressures of the saomplv vere measured. Withthe mve1• ot foumr smugPs mentionnel dlnove it wasR p:.,Al.ble to ne "air
pressures greater 'han 10 a Hg to 1$ with a *,uuewuhat greater error forsnll~er samples. Improper mixtng of the absorber with nitrogen wouldgive rise to error; however, this error is believed to be negligible,as mentioned earlier, since care vas taken to ensure sufficient mixing.
frrors in the renorded spectra .ight arise from absorption byan impurity in the same spectral region as the absorption band beingstudied. Small amounts of C02 which were present in the 120 and CO gase.3produced sl•ght snrpti-.n n or tho hih-..re.,ercy s14e of the Pn-- c_-]N20 band and the ;I1'% nm-l CU bhtrd. flv rpenrdlng .a..rLrn of CO2 sampleshaving oppI~oximateiy tne sawe abeor-+n'- -a the CO2 impurity, it waspossible to estimate the CO absorption and to correct the spectra in theregion where both the absoriing gas and the CO2 produce absorption. Asimilar correction for a)-'rption by R20 Impurity in the C94 was alsomade. This tjii ý. oorrection was necessary oily for samples large ab-sorber concentration and was easily mmae to yield an error of i * +)a1an11 in toe total absorotion except in the case of the 1550 co-i CU4 band,for 'h&ch the error is somewhat larger. go absorp'ion by inpuriese inthe region of thle cUo 4&) c 1 band was round.
The approximate purities of the gases used in the present studyare listed along with the major impurities In Table 1.
2. Recording Irrire
Xrrors in rocordizg the spec.tra arise from tha usual noise andfrom other variations due to faulty instrument operation. 7heoe varia-tioas can cause a misinterpretation of the apparent location of the zeroabsorption curve. Ecrore of this uort are particularly noticeable Inape•L.,• vith 1ow total absorption and are estimated to be 15% fur totalabsorption lees •an a10 cm-. The percentage error decreases for greaterabsorption and is approximately t2O for values of total absorption greaterthan 10 u;-"I
3. Errore 4In beasurement of RecorAx
Repeated easureoments indicasU that a ca'sful o"erator -anmeasure the ores unLer an absorption cur,-c with a precision of lsethan ±.
It is estisat~d that the over-aLl et cor does not exceed 110%for v.luev cf total aboorption leus than 10 cei-l ,,d is less than *%If the total absorptton is greater Lhan 10 em'.L.
19
S'1O I
in L-he presenc s8uay .ii vaiues or i'•rcrai. preseure, total pressure,ard cquiIvullt .rebur-e &i expressed in Pnits of m Hg absolute. Tabu-lated values of partial pressure of the absorbing gas represeat the par-tial pressure of the is an It comes from the cylinder" without correctingfor the purity.
Values of absorber concentration v art expressed in terms or a un¶tcalled the atmos ca. and are given by tbe product of the absorber pathle.auth in ca and the partial pressure of the absorbing ps in atmosphere@,courrected to standard temperature. The purity of the absorbing gas istaken into acoou'At in calculating values of v.
Since vaiues of absorber concentratiou are expressed units of atmoe",m, It !nln•v from t6' ) that the ._nitc of V'ad Intensity k.(v)dv area•os -- cm-2. it Is Amnbasized that values of band Intensity are basedon valuee of vwhich were correet'rd to standard temperature. The ob-served values-of j1(v)dv will be compared later to results of otherworkers which are expressed in units of atmoel-cmu- 1 see.1. When theseunits are used tie numerical value differs by a factor Of c, t.e speedor light.
I. WPM!TIAS 0.F SL2EjjCADIWTUI
CorICIEwIT
In 6ection I1 the concept ; equivalent pressure was Introduced andwas ex-rersed in (,i) in teer- of a crlf-ra,4nlng coefficient B, whichcan be -xPreissd as
r .~. 1,/? rD.~1
in terms of the syfubo. intrtducea eareier. The *erimectaal determia•-tLon of B ,avolves a study of the transaission of radiation throw eellsof different length in ehich the absorber concentration v In the s.The am.:in the short coli, . Lb.iUe %%foe~'&m,* .el.17 camista Ux* apure esupli of the abeorbina ma at pressure p; for thin ecel Fvf . pr~fa the equivalent preiure Is giwen hy
, . brf (rOfervuc. Cell). (16)
Mo amp5e In. Cie call* edi~ Lhw 'capii :cll-, i lt-4li1k c--rteLe. va" f nampl.. ua w he pure absorber at tUe PartIaL Prewe,,-1v C. _--7r4
t^ z'roduee an ab_-rT=" .oMc',trut1in V ..qual to t.'A?,. !a ". rery-tr-j.elh. nlitisLtly, Lbe mosorpulon ot rn&8tt0n in 1 se ayLia cc-"L to c=-
6I4C&&61Y !Cos Ulbil U&AL lot Lim Sarsr'aeiL; "..iip Na"Ca Liao Partial p1~asuraand tuL pressur.4 are leis than those In *'A, shor.ter rsece . eel'.Various amounts, of nitrogen are tten added ten the reference cell corr'vapondIno to eqi.valent, a=caur•es
e-pe~b # ri (Sample Cell) ri7
vher* r• le the partlal. pressure of the broadening gs. For thJe tmtz•-
Liou .a w._,ý; t.he aosorptions In sample and reference cells, are moet,ne.,rlvy anl, i* is assumed that the velues of Pe In (16) aM (11) are
*the self-b....de.!.g toeff-:,teut :zz *---= t- l-terLined from the relation
Ph
rf
vhere pref is the partial presaure of. the absrblng gas In the shoe.referen--e cell and p and pt,, respectively, are the partial ;ressurvs ofthe absorbing and broadening gose in th. lo'igsr saxple cell bean theabsorptions In thec t'o cs11 are equal.
The value of B vas determined zr all except the kZ60 cel CO bandby making use of the duble-besu feature of the Model PI ape-eLrimter,vith the 6.55-cm cell in the sample beam and the 1.55-cu cell In ther-farefnte UPAm. Ta-. sathod aned to deto.rair.s for the U760 cm-1tn' dc2 -I1rt,1 below Ir. Uir ;.Lc;:uunil.u ur Lhc rc~ul~a ;s'flaicsd for -thisband. The msor absorber concentration vas added to both cells by wakingthe rrtlc of the partial pressures of absorlping tpa In the two callainversely proportional to the cell lengths. The pressure ln the saqila:ell wev then increta.x-i in sma.l intarval- by adding 92 a" the apectsumvi u acaed for cach sample. The spectromter reoorded Ute &&Uo or tL-
reancamliLon of the m"plo e-1! T(ea. ) to the traunalesion of the rer-erence ceoa. l(rer. )
Typical spectral comparisons which ve.- obtinaed In thIP wwmer forLhe 22214 cul 1 kD0 band are sbovn in part I of Fla. 3 for varlous valuesof total pressure In Use oamle cell. The asthed lime at Ifea=. )/?(mr.).1.00 represents the recorder pen position wten the two beam• ere Obianacei;I.e., the transmission. of both samples were Lbe sane. It Is seen th•,ttow. tvii o•r use. b % tidcms-t with 1nc e• e Of -retrare in LLfwample ceý11 as v-11A. be erportedg, and that amo of the spectra oe~ur at%-ue
i ef i840.9 2021
1 .2t
2300;>Mo2
Pert 1. 401 Obt~if4 VeIM V a 0-3 &%W CO I&a ~twter~e.e wid "mvi co)!*, t.,4ki -4si.mn La r.tot....*
16A m ft. Tv irwe.eu. 14 PRAPI tal for oerA &Poe' %w toL~zIt&Aet. et 11: Plot of a a" couselee cr.a "CumMGeS. T160 tomr AIrtor~t O*u of Polmis eoT*W11 m to%
roalla of ua. spor *bv oft. Sc asl w ell a& toUr'sumsr Otta vi s~.awb.**~ swoIVAF*~ YftlotS~ vw*1 of mo.
the balance line for aoo frequenciea sud belo: the line fcor nthesrTherefore the total p~essure corresponding tn balance was not the str.efor all frequencies. Tho pressure oGzrenp:nding tn balance for any a '.veufrequency wan determined oy 3mtr-poiatinR oexween Tue tro succeolwveLiurvab whicL vcu~aur vat -pkya.e *.due tor Laa scaau%.. liue.
Since the value of p,, corresponding to equal tran3aission of thecells yes found to vary wiv• rrequnen;, it in av.acnat =- tee "aiof B varies throughout the band. Points corresponding to the ezperiment-ell. A-trined value of B were plotted egainsi frequeLey in Part Il ofFig. 3.
The ratio of eofluiton croon sect•zt= Is shown by the right-handscale in Part 1I of Fig. 3. This quantity Is lncludc± vuly as a matterurLtru auti rv, r t~uc t&sn It i. Isrelat*. to the Wre lr,-
portent quantity, B. by Eq. (15).
The present study deals primarily with total abseor.tion rather th:6with the absorption at certain frequencies. It was thererore desirableto obtain a nomtnal value of B which could be used for an entire band.The noninal value was arrived at by taking a "weighted average" value ofB over the frequency limits of the band, vith extra weight given to thefrequency ranges which contribute most of the absorption. 'The values orH determined for each henw, which are listed in Table 2, are -l~eved
The experimental results reported In Sections V - VII indicate tastthe total absorption never has a dependelice on equivaleut pressure Pewhich in greaLtr than appro~iaately PO.04. Thereforc r. relative errorof (4 in B vo'.uld not Zlye ?riac t'- . relat-ive arror gro~a than P or ýtin the calculation of total absorption frus. the es.ptricr! equations tobe presented later. This maxtimu error would occur only for samplescontainlig the absorbing gas alone; LhU error would decrease for samp).eccnt.•ltng Ný and would vanish in the case of infinit* dilutiou. The
u(,jjj. n.~.~ .f ~ In '.= I h4 c.rc~trc nufiniclitlly anC=Zte^0s ;.resent purpoue, which is to make it possible to account for the'±iffirmen
t broadeniz; nbilityP vf dir1:-rrzL t
'Lie 'inta report on this research program will contain detailed !a-formation on t+hr dependence of 2 with frequency ror each oZ *be absorp-tion bands discussed in the present study, as vell as for oter abiorp-tion bands discussed in subo.QVuent raports. Information will also begiven which concerns the relative broadening abilities of several Inert
gases; N2 , 02, A, 32, and If.. Bingletonll of this laboratory, as vellas useverLI earlier investigatorb, has fuda that unambiguous values of 2-an be determined und that the determined values are actually indepeateat.f = fcr the. prrppsro rango eovorod In this roA-rt. 'Nis reaulLt
indicates that the effective collision cross sections of the moleculesAre -. •eIusedily irdtlepesaeaL cf pruvtLudy. 46vLA Liu %Or PiSd.&O AAfo)- gooes used Uo Lee present ctniy.
It was shown in the MW repurt th'At thba broadeninR ability of aix,is very rearl~y tdte zim- .: "' ,) ?'2- Therefore the values of equiva-lent Pesr -are- "ncd ý'n .1-C pr.;a c. iia 6vdd ,proximmbethe total mfnl ineePui- atoThei . ;a... Prc '14- '.'a .Pata -;G'
of the absorbinz gaar is small in competrizc !71t' ý .rv'ospheý,ic pressure.
IV. METHANT OF DlATAl
When the study of a given absorozion band or region was started, it.. afound drir',ale toselect --=c dcfinilte alit progra for the spec.
trcmeter and to take all data -with the smw program. On the Model 21.0 pectxoeeter it is possible to scan the spectrum of a band With theslitvidth constant or tr! ,sm- a zl±'ý progrnring mechanisir whieh auto.matically esoluLw th 7lUjs :-_-! ncously as the sjectrum is being scanned.AlthnuO1 the oc 2 abaecy.!Vla A v)dv is indepentient of 11ittvidth or ofslit program, there are occasions when it is desirable to compare A(tV)for som defin~ite frequency fcr different samples; this would be impossi-ble ,;ýed al.l data are taken with the sawe slit program. However, sincethe datum :f primary importance in the present work is fA(v)dv, It isnct necessary to work with narrow slits; it is desirable to work withslits sufficiently wide to give large valiues of signal-to-.noise ratioeven for the largest values of total absorption. Another practicalrea~son for the use of výide slits is that. tho in-moLae of planimeteringspeotral recordings is easier for bands not exhibiting rotational finestructure; for nearly every band studied, It would have been possible toobtain sorn detailed information concerning band shpo had this informa-tim-) been Important to the Investigation.
Once a program for the slits had been selected, a large number ofspectra were recorded. The&,! spectra provided data on JA( v)dv for rx-treasly vide rtngen mf absorber conceatrmtiou v, partial pressure 2, andtotal press'are P--including, n-f course, pure ismples of the absorbinggas, for which case p - P. The vnru7of tntal 0ý_nor-,tion for -rarlioutcell lengths, absorber concentrations, r. 'u! l ,3lujt pressure, etc., areorganized in tabular form for ust ir tests of thecretical predictions;It Is hoped that these tabulations will prov.A useful to theorists.
One type of relsitionship important to neairly ell ciurrent theoriesIs the relationsh~ip between absn.rption and pressure. In order to et-ta-blish this relationship from the data obtained in the present work, L.net of lcgnrithalie plots of total absorptionfJA(v)dv as a function ofequivalent pressure P.. to then made for viarlous valnes of absorber con-centration w. From thi' r"lOpe of the curves, the relationship betweenfA(i)dv anCP, tan e t~a n., usually it Is rfund possible to Pho(wthut. .f(v)dv -Pen, where c, usualIly does not have the Tell- of 0, 5 thatwould be expected on the b6asit of (9) fo~r a squar,--root approzimaraon
Ann Lb-r set of logari#hmic plots Is then prepased girinC A" )dii ASfunction ol" abaorbee concentration w for varioits values of equivalent
LMS
pressure Pe. Fror. the stloves of the resulting curves, It in possible todetermine the r~lstts.nr b-?vher! YA(wldV ari V. It is uja~illy foUIA -tat
-A(., A...-- -- --
might be expected to apply.
The next step in attempting to estabishb experimental relationshilevh1tven,nfA(v)edv aind nauple, parameters is to make logaritkMic rlots of
m mAr)ds as a function of lPt-. From the resulting plots it is frequentlypossible to obtain empirical equations relating total absorption topertinent sample parameterz for certain definite ranges of vlues oftctal absorption aud eqaý-M.LeL- pretnsur. It is usually possible to ol'-tamn empirlical equations of the farm
[A(v)cjv - rwPalb (19)
vhere c, a, and b are empirical enrwtunts with b approxtelz r equal to0.r. Such equations are ialiel for intermediate raluns of fA(v)dv amdPe for vhich strong but not seriously overlapping, lints might be expectedthroughout most pare. of the band.
For large v-J.usa off A(v)dv It is foun, that the central portionmn? tho mbscorption bitd n ' .an n- cprtrn 'region of nar,~ ui~mplateabsorption. Furtoter iLcrease in v or P. results merely in grovth ofA(v) in i.he vings of the tAnd. 7or this situation, th: total band ab.aorption car b, Rxpresoed by equations of the form
jA(v)iv - + D Log (vPea) (20)
where C, D, and a are empirical const.rt'-.
It is rather diffioult to derive eatisfactc-y emairical equationsfor extremely smell values of fA(v,)dr. and P . Under certain circumstancesIA(v)dv is found to be nearly independent o; P., & nseult indicatinr +batDoppler browlenir•g 's the e-miznrA influence on line width; under othercnucitiornn A(v)dv may vair linearly with v as predicted by (8) for smallislues of x - SV/2oa.
Alt-hough total mbsnrptlscn Is the quantity that ins independent orsltvidth, it is sometimes les.rable to copare the measured values ofA(v) &a certain poin*• of Interes in absorption bands In order to com-;are experimental r.aults Aith predictions based on various theoreticalbund models. Pbsquw.d valoss of A(v) near regions of maimum absorp-t1mvi In 0-.. P 9rl Tt-brsw.cheq Kare t~iple" of reglonn vbtrc thcnrctical
that A(v) is dependent nn effective alltvidth; cop'trisons of A(v) ob-,-toed with differen etrie:tive slitviaths are me6aingless.
The treatmeet of data and the development of emrlfrrafl velatlorswill. 1:z ±iLcussed In s=-e de in2 thbe fallovL9G Ce~tiO1--&lOng .idt) acomparison of observed resuits and tfleoretiiaI. predictions. Manyv detailswill be - =itted in )ater Section3.
Vr EXPERIMEWfAL RESULTS FOR THE2224 cm-1 N 2 0 BAN
The yv fundamental band of N30 which has Its center at 2224 cm-1
occuIC in Lbe "atmospheric window' which lies between the strong2350 =-l C02 band and the 1595 cm-l H20 band. The major portlot ofthe absorption by NpO in this appetral region in due to the v-x funda-mental ur the common isotope N2 14Olb. However, there is absoirption bythe less commn isotopes as vell as.by at least one we"a band (VI- v,>vi~~)describid by Th=pson and Wili "n . 11o t-' aake of siumplialty iiithe prcz;..t report, all these bands togetaer will be referred to is the2224 cm-- 1- band.
Althougn the conce~ntration of nitrous oxide in the earth's atamo-phere near ground level is only approximately three part.¶ In ten villion"3,this band gives r"Ise to a major portion of Lhe atmosl1teric absorpt~io- inthe region where it occurs. A knorwledg3 of the absorption of this bandle therefore important in the calcu.lAtion of tte transmission of radia-tion in the "atmospheri. vindov" In which It. n-'urs. Th-t contributionof this band to the heat balance of the earth's atmosphere is negligiblesince the major portion of the solar red4n tion occurs at higho r fretuen-clue and moat of the radiation emitted by the earth's surfac.e occurs atlower frftL-hcies.
l than 200 spentra were obtAined by using the double-beam Mondel21 spectrometer with ae orption call lengths of 1.55, 6.3t , 40t, 6W,and 1600 on. Different obirnto" • - and h were used to provideabsorber conoe by ,una Irnm s.CA)l6t to (o. 4 amo = and total prss.'fd sfroe 1 to 3000 Bito. All spectra oer. obtained with alit widths eprren -r-!,gtv er.cxImateLy he• P10-1 anpd VITA the cell btemperature toar 30C.
A. I.33la=TN CURVE
Tracings of spectra of som of the samples bavi~ag the largeat ab.sorber concentration "r" shown in the left-band portion of Fir. I. A
Alght growth of the b€ ands a result of Increasing the preasars withNp Is illertraod by these spectra; and %be tmae limite . beyond Iloahthere isn egligiole absorption for even toe largest samples, are ,W.i-ethe by the limits m? the mpc-ra. A cutionyeetra of samples contrainingtilo1 larger values cf ansorber coan..wh.rc.tiou •ure obTAiead but. ve not
ofua tincludeda since very tttL# s4d±iou- information could be c'btiedfrom them. It Is shown below in Uol discuuao oeuf Fliai. 12 wan 4 thtethere Is little Increase in the total abeorption of ths band for larger
26
I ir--T- 0
0 I C
cli 4
LL
C~
0 ~0~
ýcz
N li !I * I I I
bi~'?tu f .Dur. t, W4v,~ ~ .:; .. i'vrm ~p
Al~r nil .w1-._=,:ZI .Y~.iML ~~~LI~L .J
"__T2 .4",W -u iaa m -i-A .du~-b. zz..
ima*2mt ..Lv. pywasuml .w c. Rrnt., G! '?, ~W!-fy CnUIL"UNU2 Jv fL.1Lr_ t. -Itre i a-u1 11il ; - i w 1 1fI f
:-ITa lu wtc~* ts,.4 ;mll -- M 1",~T $1a IA?.1W -It "r
-vu.z~~I .ji. vr uA 1ttsmVý %7.i -&--uo-n1 -,-l-r =w %f~ Wnwi~ u--
UP-t -tour.123 tc AL I-*-U -at~a~11 Prj- o .tbown- JLm 21I-wokn i - m .
Bes AI~ ~ ~ 1 C -.-., 7y1
65 ~64k
6440.2
7,5 4 0.38
L4 9 1. i
1 4I
I 7-'5f
%/1/ 1
rmH. I Iin mm
2[ 98"2 ' 0. j-04 303 -Jatmos cm 0.04
0 i mm H qW:00003 3 79.2 w =0.00024 6,5
2 -ar~ m33 lmos cm 3035 joto m3035 tocm3 5
L [L 4- I I I L ...
2k0.0*2u n 0inmmH
L0.( 4 \ /.11. 1I 1.? --. 001? ~ 2.9
-0. !13 J4
220 2300 a2200WAVENUMBER in crnI
Fig. 6. Spectt o!' the 22?'b cm-1 1ZC- bard.
K I 72qOOIl GYMS 109
41.- \\ I0054~moI561?
-I / 37524 ~ I 0 l
0w.O03ZS He .m ,'4 002002 1- 1~t o , m f -T I
05 251
009
4-.'000'l atm,, cm
110m~g m 0.001?
?45 -¶ 0.03
92 0 A.0060
Fig. 7, EA,ýc~rm oti h ý2 I1 N20 bansd.
w xi0.0186 atmo: ecm I 0
1/ II
P, in InmNP i mm Hg !0.
2- 1.5 - 26.62I ~21.6i 50.0-,I iL' II
1691.2 ii259; [V 15200a) [ 3035
O F I •[ I I l_ • ,
20- P, i" i , ,a•tmo" c mm Ho
•,"/ V 749 w i ftrser t rmH4 0 - 10 3 5
0.073 44.9
0.091 56.2
2300 2200 2300 2200
WNAVENUMBER in cm-'
Fig. 8. Spe• tra ot tse 2224. oU" lf20 lAnd.
32
p.__' _
w 3.02 atmcs cm ! 'fIl atmos ¢rnmr•L I I I : i/J40 I II I
P, i n mm - i P i n m
,L 227u0
`4 otmes cn' C atmos cm• /
Li
•O- |\ 't ,Li r5;
1 ti/ nmm fl 225
OI \ l/Il _.. • .• -
?.300 2200 2100 2300 2200 2100
WAVENUMBER in cm-!
1•,. 9. Sp1 -'r r tne 22,2. L:m'1 N2 0 &M-,
r Ii- i i i • Jl I!il ,
w z 23.7 actmos cm L 's.40F-P i /-
I \ (I* rIII ny w r, \ / i~ n 4S 5b i /I \\" -- / ainos cmI l qj . 3.4 1!/ 39 J
L 213 1 - ' ' 2.324
I 556
l40
20[ ~~33.2 2.2
52.1 51.
\J0 740w' 0074 37\jI atmos cm 0
LW w ;,0337 mm 0g
\ ~cm./ n,.mmn l 120
I4 011. -3070 -6071' 4112200
WAVEINUMBER in enm-
~47Y/ 1-- ~ l'os cm
P to mn"F. -i
II k ,j 29.2.2:0.8 ~' 5
- --------- - I I' [ -• ""*- I -T-' -T
-t o &S- t -
#,' 1"-I'lt 'l\ II
15. 71m s m4 Cl o
* ~"0
I._ L .I
i I\\ -*' i ;i .o my a
I-:~~ ~ ~~20 Z 3 mI I iI I il-10 Z m :, ..
:' i , , ,fftum s , cm, , ,..: ~~ ~ ~ ~ ~ ;; of Ic m n I I Ii l. I III I u '
36activ of rguy o~f Lhe spect~ra bave been omitted to prevent uv~r-.zrjvd.agof the figures, but as wba~ of *ach spectrum as e~d4 be pres~ut*A clourl!wa 1aoliu1*. The pzernt .. cnaeisuion of %;.* samples ta Thew spectrdkiregirm mbre ai.msata weeorm ttod can cizl±:; te estimatd by inrpoiao-tMom between ad~juatat absorption curvs.
ALU of the *zWrimattal results o'btained for the M22h ca-l N20 boadaaaave mAnLsAlo Is lbl* .3. The absorber comntratitlon v and equiwlentpreesure Pe for eahseb apJe are bhma. Tbo equivalent preasurv P. wasOaLau.IAA-! *--- th- total PreGSsur P and the M420 partial pressure p byame DIlNA oquatift
Pe - p* +~ . (21)
In seeorftao~ vIt!: Sq. ( 11) and !wb-I 2.
v.ltme of the t-ta1 abervptos as well as the obeerved portent itb.sGrPtOO at ZAO W-Le ands A213 ao-r tabul~ated. Mm two troqinrnlooS107iwpaod to the auLU~r absoopteam Is the R- and P-bzeacibee, reopetively.
FA*tM a otedAg the *=*use pwec.4wre anv melded In the 71ght-heanos.vaio at ?e table.
1. 7ML AROU'YOU AS A R302 0
MA~q of the Mouwlt2 9 rtze to Yabla e . jio.ttal =t a ~ltbIexais to P14. U, wIt~i -... abetorpt'.e aehew a a trwtiw at WI %LSJMs PrseseUe ?*. bat& oerr .ari.PDW t~o 6 61A 'ma aborher ecetootft-ttgs v al ohMs the Qft~t Of 1asreee1a4 thMPel Otdet141 Pmsn *? a"-Ing C1. Ths Ppatk- ?'f~v-e tjI- '.*** of Usth aboorpttam sell. %aeVoitah mawats a V*4~ eoiur ot *M &vwr wade of serves A *%roam& P repre-seat ywau *btj ohe*a fer bomg~a* of Pt.) slow. lb ehel otar lv em a
gtw -- " CA** *Ou~lus for amsjia .ee't , ~ %as Sa avat o i.but with a1frervat ammmet or pý &4&4. lt*a poule as th lowin *of ofeva-ft Q. It, tMA 8 weproaet svýI~ts for ou*Loe MA tew prewinvlyNM~f "p oed k; *a LA** -urwo ATr Mv m *a etg A~eb rpsi445t
tu.viv. C, sat 9 earmopooU*4e be oquiegimawet proe.
team ant mithed ftt Us r:.'iee for g up, vt 1.. J4.. It maea am a boom h S eswees to batk 14swwaut Vbw weim" be i~ovt to toVitusa *) of the valve at taftl albovpTues: oMpPQ*M tr"M "n esutiasiMoms to larger aban her eoez*tmeut~ft %ured ma *Wmee 1P, a "A L
ixvt! Is a Sm ,er *-2moso !- I.- a -arm of %as termS wis la-wlaolekIUMot P"M"10 141SmlUo 4k~~J Ue 4o"'s. to tbo tep~a~%.:v -
ItiI
10'
total ab*,:,rjLiun on equivilant pressure. This "satuiration phenomenon'can be expialned on the basis of the change in line shape with prkiAAn the ]pressure increaes, the half-width or a spectrai, line increasesand the absorption coefficient k(v) increases in the winges ad decreasesneilr the center of the lne. For pessures aufflu4enty high that theline half-vidth I-. approximately equal to the spavinig di between the lines,the fine structure of a band dimninishes and further Increases In pressurehave but. little effect on total absorption. Goody Pknd Wnimwlll haveshown that the half width a - d for N2 bands at a presoare of approxi-rn+tely 4.100 H g (Ii.), atmospher.oe), where a and d are necessarilyaverared over the entire he'd. One vould th.erefore Lot expect the total05o'rption to change ap,-Lectably with prees'lre .4n the higher..pressursranges used in the present study.
It is seen from FigA. 12 that the value of P, above w),ih 0-~ t*tn+1-Lbsorjt~ion, I am'ss uuwly slightly with lner"sitng pressure is greaterfor olarger vaiues of absorber concentration than for smiller valued.In the ease of large y, UI~e decrease ur k(v) near the liue ccnters vhioboccurs with increasing piessure does not appruciably Amres the ab-sorption A'(v) at these frequencies since k(v)u~ia $21LILaeeOUS~tlylai'ge that the absorption rengins essuentially complete at the lime centers.However, In the e~ase of small w.* a lower pressure I-, Is suff-ceiet toreduce k(v v near the line centerr to a value such that the docreame Inabnorption near the line centaes with Increasing prva-Lre is approdm~telythe same an t;-% increas~e In absorption In the vings of the lime. Thereis theiefuze ll~tlo or no net increase in total absorption with increas-Ing pressure.
Curves J thrugah 0 have RjpproxzmL*1y *be sasm slope for values ofpressure below 200 m RS. TL% slopes of s&u) of the aumsein this regisahar* a m~xlmtm value of approx~oately 0.38 and an avera~p of approzimatey0.37. Thus It is possible to express the tat~l gboorptio.u as doe finn-tior. of the 0-goiber concentration v time* ?,"-3 1for values w and Prepresented by these curves.-
That ".aw variation of the total abuiorptlon with chwnge In v aidP~becomes rary sllght fin' larm* values of v end Fe Is Illustratd by
tee crowding ef the :,umvb In the upper riA#t-b&Mn aorer at Fig. 12.This result is due to the fact tha4 k~kw~v *0 1 for meet frequencitz.wi thin tho lhas, aind hene't the toW talaorrtion at gIven by Xq. (6).changes very t±yas v "a A-0 chang. lspeoannof mtSe epeotra ofsamples with lArge I oZ? suchbaothoseInt Fgs. 10 and U, AlehamreprosouTed by the points In the upper rgight portion of FiS. 12, revealsthat absorption is complete near the band center sod that the prevQ atothe baud with iaciwasing ! and Pe ts au~ght and oc,.ure in the view,
!a FIS. k5 amrt ive curves rAstime the total abseopti-n to theequivealent pressure. 'hI% curves of FIg. 1o are itufermat fume tne of
aig. U, in that, those in FIA. 1) do out correspoin tn eoa etaS. WVl *& oifeatorber conentretion. Curves A. F -and C co•sespond to h@hearl of
I T - = -t T 'I I -
10- N20-2224 cm n.
0C ,
D//UUV rAH SML
p--J
0,4£
4 L4
I 4 0 40
Pa in mm Hg
WtfWvbS aq~dvalat presture tore.~. "Lsiap
39
U20 alone In the absorption cell, and iUhe absorber coneCntration! w Jtherefore ProportionaJ to ?.The retie Cf C v to ?a or the three t~) .-Isis different becuaus o~f the differenit call path lengths. Cum-v DýýOT
"Eonds to samp~les tomposd of a mixture Of On part 120 to Aim 112(bj volu.s), sand I corresponds to a mixture of one part N20 to k9 parle12. For curves D and Z, w is also proportional to toas for curvesA, U, and C, but the two quantities are relatedl by a different proper-tionality constant as a result of the different dilution with k2.Figure 13 contains points correspondion to several of the asaplas repzw-seated In Fig. 12 as well as several other seaiplas vhiah arn not repre-car-ted In Fla. 12 because they do2 not belong to a group of sampleis biw-Ing the ear value of v.
'The slopes of curves A, B, and C &.-a seen to dscreaa, a& In thecase of the ourwes of Fig. 1.2, for large vaueise of v w.5 0.* this* saturau", of co4rase, "-ur rol anal..Ak presures for the loinoxpaths since the waluml of!v are greater; the, m*Iaaw valiass of v use notsufficlently large to pnpiuce satuxe~t.!.u !a -'-vee D and 1.
It tosanted that curves 1, C, D, &ad 9 of Fig. 13 bawe reglowwhich are apprezlrntely 1.leer ovr i a mtIs' vie roaw of welme ofeq~ailtult pressure greater thean 10 se Ig. The Urne., y.&.i~iw of %howcarves bave elopee of' approIinstil~y 0.91., which Is cosierazbly pealtrthan the elope of the Ilmer reoose of the corme Is Fig. 12. the is..aeuses Is *lave Is, of seurce, 46m to the fast that! V m.'eases wItA tto %be curves of FIg. 13, wherses V Io ceapet ear inch ourve of PIG. IM.MWe slope of 0.91 Indicates that, ?we the Velman of WA Pan aere 1Wbthe Usear portion of these cuame,
Vre c a * a a.1 and a Is a Cft-itast. It V" abow Is 40ejisessoloof Mtg. LP that the tota~l alworpt~ft to prwawrt~oml. to P "J" awe aeffoideranbla iMWg of Velain of w MA Po. Ths8 result &;Lost" tas%the eameent a b@ftid Ism.stIatl ebove .sa1.e 0.)7 "Ae a wareteee" ieas approxiemlely 0.5%. It Will, be oba I s atoeseinei of 116. 14
tn the to'is w a t-soVis Is, is fact, appradnately prevetuesa tov~l~ O~v er U6n im lof Vae"S of w "e to aim repemoesated b~ythe .Iccar partion of the =um f7*.1?a )
It ts not"4 that the *Laupee of s raes %. C. D eAt I of P1g. 13dareaso taowa'4 lkr vaue of P0, for P Lees then appmdzaistel10 ms AS. Ib~s Ucrvee I& slope Lawrd 10T ber ~eoeeuro cas-t asplalsed as the basis of a Iesi comisatlng of Urns beei the Zonatetstep gives 67 14- 1he Uscs 40C1"In sloPe Is a&t~rIbtw4 tW 00.PiUTbroas.slug at the lIme- Stadlcr det,'vIow. frre MAe &.poctsd beeftlesOf ten etU ee 001 O f O areatng u- %Qfwr Obeew-0d W 6004Y amd .~rMOUIs a study of the _'161 *,A LM6ý CM~-' 5?U boom WA gore attribs-.04 to
F T�fl� <T�V rTTF-t-trTT Trl,]
F -i
I� �
-1�'1 '3
0
\ \ \* ' ' ' 1* '�\\ \\ :1 �
\\ \ -I
\\\\ \\ .43
� � IIA *
5 4i$
* L *
�.i. * U ..
Doppler broad--, g. Benet lctl 5 et al bA-e .. !Lo shc'wM that tte Pntzli'u-tion of Dopqlxi bvv*,.ening Li5 ýh P-turption ol a i~ne or band vccviso!nportant at pressures less than approxinstaly .0 - Hg, causing theabsorptioa to be lager than expected rroo the Lorentz theory. Theseresul.ts are co.,fliuwd in the present study.
There are also inuticationn of a decrease ia the Slopes of a fewof the curves iz, Fi g. -'^ at values of re loes then approximately 10 m 11g.However, these curves in~lude only a few points at lower pressures, andany explanation of the effects of Wippler uijixeening based on thesecurvc3 alone would hardly be cenclusive.
In order to illustrate the depende'n- cf tenln! &bzz.rpl-on uponabsor'ue;: iýje,;trstion w, values were tAkenfl rom Fits. 1ý an4. 1.1 andplotte-1 on a logarithalec settle In Fig. 1ls. Bach curve correspuniis to a!onstan, value .)f e;ý.-.Rent~ ;-enz-are ir4L cated In ).-dcz from top tobottre-. Prme the curves of Fig. 14~ It Is possible to determine, thetotal absorption of any asumle for which the values of abacriser o's'sPe.tration "u equivalent jre~ssure fell within the rang covered. Forsamples baying values of equivalent pressure which lie between vale.uscorr*@pon±La4 to the curvest, it is poesible to lnterpo.&t.. The p~ointswere ouitted In order that readings from the curves aIgbt be mad& morereadily. Each -~ar'fe was 1.%swv% ever the renap of absorber eoceeatramionscovered by the Ista.
The love r portion rf the u~ppe.wS..e c"* u inFi#. !- otsc'n correepooto an equivaenet preessre of Y= =m g Is mesa to 1be Usear vith a slopof apprawihstl~y on, thus indicatin. Utlinar dependtene on v. IMlieeor Amnendenee oe v, eaut, oe enl,*4 on the besis of Sq. (;) forsaeVpos such thAt a~vjv <<I for W.l frequen^1o. t~t!Ar t~e Tendtilon4q. (6) con be written as
JAvtv.j 4
wbe~Ja~v toi the baiv 1,ansIty..
The ctrfldlt.!e h~v)v >> I ý& attained by keeping ! very awl I wittP utftcientIj !&rse so UL.,a k(vl to mull. even nar the *"~toy* of
tLt mi-ctral limps. The cood1Ui~n of lar"e 7, end smal w are "1tofor the :*Spor regloo or the top rurvo It P24.. lb. Prom &4 (6.) tk.linear &POW4.no. n" V ts MOVIO"O, a"~ 1i't 1 ;;s. that theA value oftfe q..ctntlty jit~v)dv ;&& be detemeloed gmpbl~aVy from the absorption
&,aa0*# n4 Y§*9*~wente4 by the linssr pwv¶±-c :f b*t-cr%
62
At the interce¶',t uf Ve. upperzoat cufw. of F'ig. 14& vith Ube onlrmUea.sis, A',V)AV O .3. ci' 4 one. w - 2 x IC atmcs c~p. Subutltutioi. .fthose values into Eq. t(l ) ylelds it value of
fk(Y)4v - 1850 atmos 1 10-2 (23)
for the band inteiraiy of the k22 CSm N2 0 band.
?be value ofrfk(v)dv given by Eq. (23) can be comared to values ofthis quantity which MY4 b~een publtishp by other workers. Tb. mofulteof three other vurkore are a@ fol los.
voserver k~v)dv in &to- ca.
ThorvAike and Wells" 1867
CRUaDL-m WKS" ame ThONFuý 1617
Igpre W.4 Crfori4a 16cr,
IS ordai* Lo fimA the valua off6ý.)A .y' the motbad outlay*& IS thispreseit etuti, the ajrremiution, tht 1kv)w << 1 for all w amst to valid,G vFq'AlxeMMIt whiCb 10 Satisfied by 6=1 vOAMSS Or V &St VabIMS Of Pswft..1.tly large so that k(v) Is emll, evem iwor Th* -eaters attiUses. Vadr these coSm~Uum the Ilaw or the, bamd are sad to beOemlately %,roSiwo*4 NW tme total %beorpt.,es. Is Iden tofpre-
V~k.tdata %&Loh imebda soewfioatly V160 e0ps of V Said 119 itIs diMetu1t to t& sure tus% Use eesitloee of "all v atA lirp P* 1TMAMt~c4%tl~Y 10*11 e4t10104 00 tht the *pproximtIceh(v)w << I tovRlid. KMG tvaetUs %e0 &*atse CeOWrs104 the Pwesdt. OfYordkasi Wells. vWich van matomod sibo-to with reprt to this approxlmtiee 1 7mLawever. I1. the pueeat Stud~y euftieie..t dAta are avalab~le, which tail.
Wee thet tho art-Omtl" It Irnte4 va-111
Use Oft-wami Peroute of Use mwpr three crweet, vbich Oarrepo"AuIc -"'tee of F, > PIO m ft, toinerlp. Therefore am *omlvft Uthufor tow value ;fw a 2 O a r 4bmm ftMod to eaelt~i~.Lbe
-% * * L - 3"4 m inmed Wae etatteteatl~Y lare to Fradwe ioe~Jtetrmaiksag.
"th eoquiremat thet V to eall io aaro~u.7 mUefled elmee theiwnr pertlm of tho w~r 'Pwva of Pe. lb to liwoor wIth a slop ofvery wrly Visit . It Uwrvfote &6440 "th"a asespsey of tae valueSIT" $%- 211 lapsasi mwo oa the accuftey with *.1ch ~bo slactiavont masaer*d and %he acturcy U hIe-h w w%% 4stearuisl mUwhr u, vs,I%* '-SlIdty of "he arWredMtl0 wthaLt h)v -oc i.
163
The spectra which corresr'nl. to the portion of the curve 171 P'g. 14from voich the readsing ws •akeu were recorued with thc ordinatc sý.i:expanded b1 a factor of ten. Three spectra were obtained for each sampleand the average was used. The short absorption cell (1.55 cm) was usedin order to produce small values of absorber conzientration v withoutusing exrtremely small r•rtial pressuze, of N20. Tn order to improvethe accuracy of detprmining !! the N20 was adtted to the cell in theform uf a mixturp of WýO and N2. This procedare =L it possible todeal v4.h pressures sufficentaly large that they could be measured withgreater accuracy. Consideration of the total absop.Ion meaurements%mAAzatec thit .the -iuluc oft. (..) dV g'ion by (23) is accurate to
D. ENJIRICAL EQUATtONS: LIIUhTION
'the zurvea . f Fig. 14 are seer to convergR at the lowest and higbestval--f! v, 'Au, tho five 1-.Žiruar oi a aw ..ro y 1-4eer an.4 pars-11el.
over a wide reuwe uf v acar txeo centers of the curves. The slope of thelimear jpurt!."s of th; -,res we fomnd tW 4o approximately 0.53, thusIrztcatla that the total abeorption is •oportional to vw- 53 . Therne of vlI. , -. v ac, P, for which fA(,)dv is proportional to vO' 5is approximtely the sme s the range for whicb fA(v1Av wse found tobe proportIon, to PeO.Yf In the discussion of FIl. 12. For valu•s ofv and fe,. thire .re revnesentea by the a-er portions of the curves ofPigs. 1- and l1. theme results Indicate Uat
JA(v¥d. • v•', " .,, ._ 4[ve.1J 0.,)
*bere t tsa constant. ?b ribult In %,. (24) i.s se to be In goudaloer wlit 91. (;2~), Vtlch is based cc P.9S. 13. It Is zwcIad thatthe euree of fig. 13 arn based oe dta obt.aLard from sai-i of U20alone ad esupt.e of E20 nd ft vUeb were almed before beingm L&Lvrec
to the - I *vte of heM eurree of FigS. !: aaO 14 are imeed as heteetta1W4 :.-Ca tampleas f'Tft b$ addlng % to tho abseorptio ceLl afterth IL.0 bad bse introd•ucsd. te pd agremnt bet"en te resul-t o?fig. f nd ".~ of Figs. 12 axmA 1" therefore iadiloetme that veryUttue enor In seuphlia me ketruioa• la the prceeo of addIng I; to
)rp Pip 12, 15, Ad 1. lu in seemn 9Atat •vet emple, Nnectlawoald be req.nJ '", ,.lata the total absorpta o v and Pe fo t
alwue3 0f thase parmWre. Several ea.Vrumterv 9?s oled:= auiA :,Lx*1'c -.4rexzcie. "ta Ujese wene onlyr valid tar Unifte. vYtteofy a.1 TF. as i the esae of Sq. (24).
is thU .M report, wo dllfferent types of otustIose were ee4. A"wftk fit' eWtUoA -f *A- ftrv
PJA(v)dv - c W12 p..
vas used for small values of total absorption, an. a "n.iung fit" ofthe form
S4(v)d . C - D 1o v + K In, P, (26)-J
was used for larger values of total abscptlon above a certain valuecalled a detrmining value.
Oaluoe for the conjvtarr r-, k, C, D, and K me v1il as the determla-ing value were chosen for each band to give the best fit vith the data.Equ&luw (25) and (26) wer intetwdet only as empirical equations witathe conztante having no particular physical or theoretinal signficance.Sinee the dAta. pr"eMnt.0, In tho .•,•,mnt rep-r• cover such wider renepsof both v and P, than those covered by HW, it is of Interest to usethese new data to determine the regions for which equations of the formgiven by (P5) and (26) are valid. It i. of equal interett to demonstratethe short-enmings of such empirical equatiops and to point out the dangerinvolved in uning them to exarapolate to values of w and Pe not Infludedby the data from which they werp derived.
Equation (14) Indicates that tb, •t"tl• ^-tton is a functinnof the product vPe
0 7., at ,enot for certain values of w and Pe. It
order to cheo the usefulness of a function of vPy0 ' 7 for all the dataudoitned and to illustme I, 1*flcteuu. Lth c•urves or Fib. 15 havebeen drawn. Each ca-Ne corresponds to a given value of Pe as iadicatAd.The points shown in Fig. 15 do not rypresent actual 9e.sples, but corre-spond to valuer taken from the curvea of Figs. 12 and 11. Since eachcum corre"ponds t^ a given value or cquivalent pressure it bas taesamm shape as the correspondang curve in Fl.-. 14, but the relative pool-aions of the curves are shifted along the abnceissa. Some of the curveswe,- =.,t etended over the full range 6inne sevoral curves would be so
- *... .- . .... hn . ,•, , the :azzlte curvl %are
not incl'tied. all the rolot.., were lneLad, icad Itut-Lu .bere the curveswou.d -:,ccux.
It the t~taL abrorpy,!or, were a function wre a functtion of' ataly thepr "uce• vur.° tfnr allt "m'uct of w ad Fc, u uurvuu vr Fig. i. woltdall coincide. It Lu no,. surp•rwing tot the zurv.. -. rresponding toP, - 3000 m fg occurs well to the right nr the othere mince the finszttztur4 of U'A tz ..'rly suooUitd out at this hIgh pressure ma4the effects of Increaeir. the pressure aRi rua~l as Indicated In FPg. i-.
It it lntt•.rtin 5 to n.t•, hnt. tho ,lct" 'orreeponndJo to P* < 250M Mg oeour relatively close togather oc valJo'n nf wPOO,7 grater thanapproimrately 1). (-at,%i cm) (mo 4t,)(', a ree,it iadiiat.ng that rer
'5 tmm
n o 0
q0
A
46-
1hir Tregioii of veJlue3 of vadI the totý-i absorption cou~d be app.-w'i-W-ted ý' a k~o~ .r WPýý.'t.Isj~e i~urvu- 'orrem-powiing to 76U= ibgalso converges with the lover pressure curves for values of ve.greater VhAn approximately 5, but this curve fall- definitely belu.w theothers for smaller va-P.. ,,R07
Mi'e icier portions of thA- ourves diverge, with the curves forhigher pressures and lower ab.sorber cconcentratlon falling below thecurves for low- r pressure and higher values of absorh." .oncentration.This result ia expected on Lhe basis of the lover curves of Fig. 12,for vhich the vulue of absorber concentration Is suall and the Increasein total abeorptlcn with increasing pressure is slight.
Th'ý points corresponding to all the values of Fe except 3000 mo Hg"ou oose L.ou LLie lu Lhe rarcn;.. iiat upper portion of the curves of
Fig. 15. It should be noted that the closeness of these pints doesnot necessarily Indicate that the values of the e xponent (0.1) to whichP. is maimed hass been determined accurmiely ror the values of! V ndrepresented by these points. Since a change In the exponent would causeonly a relative horizontal shifting of the curves of Fig. 15, tbs valueof the exponet could be changed considerably vithuut appreciably alter-Ing the, crd~inates of the rather flat portions of the zurves.
The upper portion of the curve corresponding to 10 = 4g rrosesethe curves of higher pressure (except 3000 -m 3g) sad falls below the.This Indicates that for theme points the expomant of to should be samswhat greater than 0.' '. Thus, ore t-odcludes that 0.7 is low for @ammvalvies of v and Pe and too large for others. but It Is a nominal valuewhich can be used satisfactorily over rather wide mamps without intro-duaing serious error.
From Fig. 15, It ts a simple matter to deteraine graphceily srnmsimple empirical functions of the product vP* 0 ?7, mand to determine theveiu.. of v and Pfor which each function to valid.
fIeI middle portiorni :f these curves which are nebarly Uwasr ca" 'asrepresented by the folloving equation:
for fAvd - "S.0 PO T .o*10 <JA(wt.'v < k.5 cm 41, (27)
IC < P, < 250 M a#
Equation (27) in the "mes an Kq. (?ik% rntep the *=%nant a of (A~)lAs been evaluatoed from the .iur%-- oi Ivg. It% &M sIubatitut~at Into theJ.MLt~er eqauationf.
For larger values of total absorpt~un Lhe follewing equation, *tiohis similar to the strorg fti (26) of HEW, kiAM iyen deri~ved.
rfor -t~~A(v)dv - 15 44 lag bg .C7)
WA 5 <JA(v)dv < 120 cz-1 , (28)
IQ, Ile (76UMN .~
VaLas -if total absorption ealcutat.4 by use of Eqs. (27) and (28)are believed to be aceuxato to appro~idustoy t 10%.
Seweral 1nvwst.1eatnr@ K.ave use.d fumcttoraJ of vpa to repr-sentdal-- v6*.-h -.1de ~lo f v %ad ?a ::=*r~ng ="-~ smallar ra~pethan in the present atAy. i'brstore, the lilmtat~oa&o cf tbe use ofsurb fiunctions were not Il~ustrated bo vividly as to tb. joz'.est st~ky,it &L.au1.i b4 4k*hupzad that empirical e.qiatUýa involving aL twwtloaof v?96 eannot be used tor *%all valusy of v/i1 or for hIL* pressures.It Is, tberefove, s&uggested that caution shout! be 'we wkin aj1044the eqAUstow lsted IMa the M report to samples "at ore SWI.Ior themthose f~s which the equations were derived.
W. eoa"Jaw or =ITii."wl "M
UM MOU M m W 1*5
it is rmsU*4 .1m Station 11 that rto cortala vives at v *Ad FU*stroagJI-w approvismt. of te alasesoer budi inod~s!t &aat wM
the total abeoartlOR to a fA.et-04 Of V1.9 . as"er, it bas boes obes.t. the Jkle'iois swettles that a Nettlesa of vPOO, fto" MuthM1$20 asa avr reahAr vii. mapse of wive of at Oa pavmool. It totie refore of lataemo. to sho te ftI&towblP beltwee Urns totaL %heesp.tios of tae Mif W,~ y0 WeM a the Product v9ý
Is order to emm thi *Ulo.woki &rPb&&e5.& we Logaitin rtOkse touta Obe-rpttos was P164*4 tin P14P. %A awasest %obe laft""m ofwt'1 tor the Aleteree. prooeesm lietei4. The peoita SWO to 14. 1h4. mot OorreepemI to *"*I&* ateastyj waeute. bat to value Ubwe "vitk" cw-fo of PIP. U, a" 1!- ft this Pro,*~4MIN It. fte PoeftIb toobtals "ets Of postat Wbelk armeeorow to aL a-*& malo erf?a "as mam tor "~. Ilk MA I!. atome ftet euwa ev.rvepea~a *L a gtwee walmeOf eqwiw..ae't pm~r**W* J% WW Lhe e~m ~hp as *t. aafernspmi~e aw
is Figs. 1b and 15. but tUe rtlative positions ot the -wivos are vhitt44.046 -,A ashclasa.
% lb.Jitreewt crwves tcarspoe~las to ~I&I04 'e 7,Gsem very e~os" OPthsr to tas "G~o Sr'enWmsl?4 te vI &"star
I- I - P
V -�
-1
� N I U
-
j.,**� \-4
1Ap.6*
b
IL ' S
A*1
L \�'s. \ I. I
iaisstII I')rI..4
S V I* -JI
a I a )ajLL I- .
II;
hamn approxlmately 500 atmo-3 em x = UP,. This result. ind1-,A-tes that :tis poisible to relate the totAl abburption to the variable vP, tnte t-
vhat Inconclusivo, -Ivnne it was shown In Fig. i5 that. t:e total absorp-Lion of aampLea tInvolving the aame values nr v and Pe could also he re-lated to Lhe variable vP 0 .'". Ini the d-3w3ublt, of Vig. 15 It bfei pointadout that for thene nampLen the nbororptl-n Ja nearly cowple.e, and t.hatthe total absorption of the band Increases only slightly with in-reas-ing v or Pe. The tu.a- absorption can t rwofore be catisfactorily rI-lated to a function of vPea, and the value of the exponent. a can bevaried considerably.
The curves are sclarited considerably for values of v and Pe forvhich the absorption Is still increasing with either v or Pe. This re-
fartorlyv ruuaetpe tn tho ni.nalo vrifte~f is.7.w-a +.! of interert
LO look 11 &hiu La L aL th46 iegviab of we curves of Fig. 16 foe whI-hthe strong-line approximation vould be valid if the absorption band beingstu.-lei cou2d in !.'.t te reprecentedd by an El.s-acr band.
The regions of the curves which Are to be lnvestigated can be de-termined from curves and equatiows g/ven by Plaas9 for tie region of"validity of the strong-iine appretimation for an Elaz!;er band. Beforethe present data, which are given In terms of the parw-eters v &M Pzocan be compared to the thheoretical predijluias, It 1: necessary to re-late v and Pe V) the Itmen.ionless quantities x and ft vhIcn serve ,.otho variables in the theoretical equations.
An Indicated ir.de i'.tlon TI, the quantity x Is g!vea. Ly
SR (29)
the parameter A is given by
vhere d in the frequency aepnrati.•- of adjacent. abooplcn Ulnes. Foaa given band, 13 Is proportional. to a, which In turn Is proportionas toP, (Eq. l4); therelor- it. is lActssary to :1I= the conztant relatingthe two quantities 8 and Pe. The vaLue or Lhe proportionality constantcan be determinoo! by using values of a and d for an 320 bead, takn frMan arLicle by Oood? and Wvrmel.11 menticned previously. The vslue u*ie:W1 41 wU, 0.04 cm-.- nan c i vwn- n=,imed to so propor.linal to y. andequal. to n.r c,-i &t, a oresoure of one atmosphere. Thit.:ore it fcan be
2/;600 (31)
50
where U•I s expreseed In m Ru.
bv unhiis' I'ir. 4 1; a, a1pplivne who eg'n11'.i~no alvn1-y, 2401-.the v•Ildity v. Lthe strong-.ire apprbxtmtlon, ,f1 Pn Flolaeer ber4, i.t13 possible t.o determIne regions of the curves of Fig. V4 over vblchone would expect the total absorption to be a function of the variabtlevPe, ac-urat,. to i5%.
Fvr example, for P.. < 2,;U = Hg, the total atsorptt-r. Los a rne-t 6On of WP, aecurt4 o 15% for values of fA(v~dv greater than approhi-mtely 60 cm-. an4 the relative error should decrease as the total ab-werption Increases. At the value of vPe for vbIhc the curve of Fig. lbcorresponding to 250 mm Rg gives a value of fA(v)dv equal to 60 ca-10the curve corcp;nding to 10 m Hg reads approxlmtely 71 ca-l. Th.wit Is seen that the total a'uso'-ptlona cannot be reorebented. with anaccuracy of 5f. as a function of the slnrlo varlah. vP fa r r th. V•1l!t.
w %,-, Ile tr-111-. . . hc F~leasser lAnd model. Th error Ie een %obe more nearly 20% than 5$. Similar deviations from t*.* pred~letel
strona-line dr.!.ordence vnrS fnrn.i r^- ntber v,:e: t.f Fe.
As jub:. in--cti1 the dep--en~c of the '.W'~Al absorption of thisband on v and Pe cannot be deseribed by a simple Elsasser band, and canbe described by f u.inl:e empirical equation only over limited .-a4pa o:Pe and v. However, the total absorption could possibly be described Interm oýf a "random Elsaeser model" made up of two or more EZlasser bandsof different intensities. Su:h en analysis of the 9.6 ozo-ne band hasbeen made by Plags9.
rrm tho previous dWscussui-n It etn be concluded that tht wotalnbCyU~of '.L 2224. cu-l XN.O boint Is less Jep.enleta upon F the'n-
v fvo essentially all "'alues ;f v and Pg. Tuhs Is in contrast to anElsaa,'.r b'nd for vhich the aLiung-Ulne approximtion is valid over acnnsiderable rangeof values of v and F., and the tots-' absorption hasthe same dependence on both v ann Pe.
The low dependence upon pressure as coresred vith a Elsassaer tandcan e-Y explained, quelitatively at least, from the fact that te spectral
- -. - '..r "j' L."Onst; 40 na~uuad for au =16666ar be06ni.
Much of the band where the L'nes are veLk, for vhich (8) Is aprozi-mately valid, and vherm lhc .=:T.t of Increasing pressure Is smai• hlethe arrecir of intreasine absorber concentration is lore*. Unless allthe lines of the band are strong, the effect rf "-. "--o-"-H" elvany be lecs trI. the aff*eý *., Ii atlslu babsrber concentration.vh~ch is the resulL u,.rvvd In the present study.
51
rF1JRT1R TESTS CF MIASSER ýýDEL:ABESOJ'TON AT R-MkX, AND P-!IAX.
5ince it is pro~able ttt ti~e abs.crptiofl by Veftk i~nes in the virgsor the band contributes to the deviation of the total absorption forma strong-line dependenoe, it is of intperat to i~nvestigate the absorp-tion A(v) at the frequencies of maximum absorptl'mn in tae R- and i-bran hes,where the strong..line approximation might tw eupected to apply. Thesetwo frequencies will hereafter be reerred to aq P-t--. o~A Dmtre4 ;ctively.
Mhe maj.or por-tiou oi t~ht7 absorptioin obsiirved at these f~equencies&rises from the spectral lines whose ce.t~ers occur v~t~hia the spe,!tralinterval passed by thet vipectrometer. If one could aivso that all thelines in this interval vere evenly spaced and had the #am half-widthannd Line strength, one would expa.-,t that for a .- ertain mapg of values
dicted by an Eleasser model. However, it was mentioued above that. thespectrall region under Investigation --.ontLina weak bands as well1 as thestrong fundamental band. Therieforie a portion of the .ibsurption obeervedat frequencie ti of yak absorption le due to woak lines whose ceavereoca witaliii the spectra. Interval of the spectrometer. The effsect ofthese weak lines would be to cause the obs3rved atworp~.on to oeviateinewbhat from tb- ou-iedependente.
Thare is also a c'onta'ibutiun to the absniztion hy the viag3 of spec-tral lines whose vwontur~i occur aitside the s@aectral interval passed bythe speict-rometer. However, as was disausaaed In Section II in cocaimtiomwith The RtzrcnZ-1ino approxLzation, the aboorption by the wirjs or a linehas a st~rong-l~ne Iepen4enoe. Thorefore, the abeomptto. b7 Utis vhos.cantAirs &Av- outside the spectral int~erval passed by the spectr~testrwould not toe xpected to cavse the obeerved ebeorptlon to deviate fra
Thm ml,,4t of the abeorptloc (2~ co-) ^,m A(21213 co-), thefrequencies correopunding L~o P-ma. anI -m.,iespeetively. have beentabnlated ftnt *a,-h sp4.-*.ru !. Tsble 2. The £rve.&nc;, of the regloesof' Wertaum O'n-TI-.1 M)'trfAl vov a1pt*) mu& Qh.repe .0 6%0 I'A~tA
orbaoged for diffoivan values oif w end P p 1'ut toie difference betwiton themmria'. %bsorptiou k=d thAt at Goe two 7 requeawiee LIst^4 Is vae,eince the elope of the abouri-t~on curlee Is em1l near teOSe "~100m.eiBON of Lhe absorption curvos, su42Y as thee. to Fi, *,. 4o sot bass ve*distinct. av.-rnttn,% wvv'ms, %r -i stt TO-~t ettri the value if portentabeorptivn wee easaured £1. th* two frequencies desiguaed.
Itha values ef absorltron A(:.,40 cm-) of several of the swqiae are
t% a given val'.s of v as ivdIca%&ed with wx' currvapooding to cam1seef' 9,0 alnos and tte dot,. rnrrespoaiiae te' asupl*aibthvi*nx M,- *190 tutr.: RaC'. The ý'try"2 hav- -to -%me- grarwml rM4&gs L.- " t... in Fla. 12,
I,, -,I l •• I I i l i • i 1 i . , , uI I M i I iI I
iop
o 0.\\\.
J- -.1 ,
*" \I
•\ \ j 1
oval 1
S5 -
it% .;1iuri td.w~ a.surr.of Vas plý,ted aEAUu st The slopes oithe curvem doc~rpsuqp Ovt high v-'-!P 'La Ulelz~ ;:s.e . 4h rva,:
A. lO"i Pbsorption ýcr large vallies of w an Pe. Severa ofthe cueves have portions for 1,~ =H < r~e < 206Cm Rg Atich are nearlylinear and approxiotely parallel. The sl.ope of these portianE of thecurves in approxisitely 0.41, 1UcatiW. that the absorptior Is Airnper-
leesa to 041 It is notedto ,toP~lIdpnec I infenllesstha i~ P,,5 eredene bIch is azaociated vith the well-known
square-root approxinstion.
Thr re seen to be a. slight d.c:. esqj In :.-c slope of curm K &ad Lat e4LIvelent preesuriee leap than six or eight. me g; thiw* Ie:reeee Inslope probably corresponds to addttiynal absorption reslting froi
Y~prbroadonine..
.~ aDe.zy~ifl -4u a-' ý at m-branch swertami uv~s flotted IFi g. 18 against P5 for the samples for vbich tot.al abooryticm is plottedin Fig. 13. These t; -i differ from those In Flit. 17 In that eachcurve In' Fig. 16 does not corneal m to a Viven vau of v. but v In-creases In proportio'n to PIG Tn *ath sample v Is proportionat to IP'but the ratio V/Fe Is amllor for the temple r;epresetaed by each sulcesiwe:urve. CLrvwes D, ~2, D, and h9 are seen to bave nearly linear portions at'slopes approirluaely 0.91., with 4.ctroaslna elope for l.arger val-me %Xf toPir whicla ove~iap- of the Uses teemos eli~ficast. ~Th linear gW'
tioe o th :u-msstivgsst that the obtorptiofl Is proportional toXPs' whore tb* ,tm ý. the expuasete a and a is approxleataly 0.9Z. 2Uereektit is Un be mwared With tbe Prediewd ,Iltuer-woot .eoCLa over t *itt, abso)rpti, on prointportional ý, 05 0-5 no demee Is elop of
caree B. LO. WAd 6 ot Pieesourv beli 1,5 - H Is cubt*4J3 1im.to Doppler broadening, es, in te :uaees of tn".I absorptloe In Figs.12 am 13.
As Pstate earlier, thes abeorytloa -ma w reprwaeeted ey the single'marltable vP, for "mluse of v send P for which the strong-Uii aorwowi-tioe to valid. In ord#T tasov shw tisepeafence of the oheorw4 abearp-Una on thM vmariable vE,, vvalues of ebsorptoas AiMGt am-) wcre takonfrom the curvas uf Plan. 17 sad 18 aed plott*d a* a Nnetic of vV InFig. 19, vt~ere *each curve :orropoedo toe 0$Iw value of squ~aleiat
In vhteh. tho nr~inAto ropree'mnu v. -*oIo ho- t~an peri...tabaoigit.t.,P at a find fre,4 msaey. Validity of the etrowgUna qSWIAu-tiont wuld, v! ec¶srae, be ropraeat@4 I.. rL.. l9 bW a aciuicidwo or WOecurves oorreepoiwting -o th* dt~fI~.vew pra-o As Ia the 0aee @t ?fg..A~, vhia s to mUar ezxept Ube, to-Al abeorytioa Is plotted as theor.Iimta, ew..e' ur tho c-urvves.. coseen to bloor prec ve @eto the rt&t or and Lolow the evivae corroeprwlhbtvI I- tetwi preewIs.The curves, cot respoaidlag to luwer proosivve tead to *ftvero for Largvalues of w. a Moeult irticativw that Cur Jwtit vokuss of v art ro the
t-to oh,,tio c N.l O ..- 2:ed by a ýtrone-'Ins a;4jroxaiition.
F>) 00 ON
0 Z~
ICC)
I -t7,
1j V
ua:Ia u
I
I
-L
-1
B.S.
r '�9.
. - V
1U
h.
.� 2 01
I- I.
I!R 0
ji�[a.
I 9'
IL.2�-. 4
Mha three curves corremspondin~g to~ valves of P0. equal to 10, 21),a~nd bt) eve Ng ontain portiorot :trnight vqth aVL~ -.i2le Is alpruxLmatel k).;i. rrý resulL ;orrenyonax to tneweell-knman square-root di;teu~e on vi; however, It In apparent fromthese curves that. the dependenice on Pe is less than squatt-root sine*the curves corresponding to hiphsr p-val-w. ceur to th: tii.l of 4.hn~ecorresponding to luwer pr--suures. it. tn almn rocalled from the dim.-cuaslon at T~g. 17 that the maids,= deppird#ree on Pe, toi ny apoxi-mately Pe" ~.4
It is noted 4&at the w0. 50p*0..l a1ependenre' which is found fromF,I--, 17 and 19 in consistent with the result at Pig. 18, which Indicatedthat the abortion m- pro tiozal to va Pon where am ; .2
Curves similar to those in Figs. 17, 18, and 19 were .Iirsur for theshsorptiaa A%12211. L u. r~et.eair.; curremponding tn marist atworp-tion in U. P-breanch. ?he features of the curwes of Fid. .10 are similarto the corresponding curves of Fig. 17; the elope of the straigbt pro-tiams or tarn curves of Pig. 20 in apuroximaely 0.6 which is slightly)AMA than the ulue* 0.161 cLtIA.M In Flg. 17. The result Indicatesthat the mainmn depelndene oa proacure is slightly loes tar the peaksbsaortl.-n In th* 7-tranaý tmau lu LL% ir-brsaneh.
"wb euirvs ot rig. ;... are also simdlar to tb!. eurves Qf the eerie-spoaftim Fig. 15 which rerreaeusat the A tramat 4bsotpt~ioa. ThW s loesot tbc straight portions of *he eurwes in Vigs. 18 tad 21 are sessntmialytho eamm 0.92. Similarly, the features of the curves 4C Pig. 22 anelike those ot ?I&. !';, bowc oer. the elope ot' ý!5 rtialdbt portios ofthe cames of Fig. 22 **oem to '.e %s1Lgtly greater (,.Insto" ofO."0), altbough this small difference Is hardy 10 slloieat.
FIgurse 19 saM 22 !omllcate hat the stoorptlou can be rejpveaeats4boy the strw4g-11 approximaton ewly f--r mm. valumes f re a&I verylars values of w. For smaller value. of v amcb that the abeorptioa IsPrwPortine-al to ;0-5 the depseesive oe P', Ts sipificantly lose, uAthe strogmg.Lir approxiaitiua Is &- 1ýmapr valid. 't to or Isteroet to"Gom tbe .. tuwes of 1Pi0. 20 aug :' With theoretaLol results baseg 00as 11" Faee 10GAAm As &a sm 1 WON =W f0 .M dom VIVA *J1M euzs OfFig. 16. It was possitle to vAM. :tu'b a ImpArlsoo by aa.'Iiu* Ube re-;aU.,Mshp betweem 0 OUd P, 4ML U (..Vone by Sq. (ý*) MAn 4ajl1y% thecomitlons girves by ILaee.? for tbe vrAU4Ity of the etror4-11me apprCmi-
Par gosiaplif It r. 550 sm 94, U.* &Uo%#rVUue of ea LAse"eer boAtom be sopraneo as a f'iactloo of wPq within #ý% for vaeins, of absorr-tine greater tham, aft.Alotely -(4. Ir se~wpmrlag this witha the earve.af `Lt. 19. 11. 1 Ad that L10f" Vý 0,-- equals5 1L;,~-F"1intelY bi% at P, - 2¶fl VP 24 for 1he sup Value O~f up# Ubich gives avalue of ýC% a~beorpti -a on the IC s No scurve. lk,- O-- It aft ab-r"s4tq.Ative 4,lrti5vi.c . as comarv,4 V1IA UW VS." or I'S bead '4
I I I I I Iii I I II 1. .;
I�L\ \ \ \ I I I I Iii� I I
� \ \ I
-t
r� " " �" \.\ \ \ " -�
\ \ IF\\\ \ \ \� I
I \ \ \�
'A�.
14 I I i... - 'S
1.41
\-0
* I
� \ \' \ \� \\ \\ \* \�:I-
- NI
? I .��d!w4 \ �
K .4
J** I
.1...K .*. 0�
10 1 -T- 111..u,,... I I IrTrT
N00 .. ,--'
7 E.7
/ US ol
.-, j- 1- 1
4~ tSS0 4
in mm Hg
Fig. I -Ar pmrwnt eb~orytlom at, '.f.; t ", ' t*VUL s"?41*1W.Vs
tenm pftflv.v for v" .*%vi utxs n:s -f & wloroe~vtfltttn or* r;r:nt ~ - L~n
Q
El
.1,
[I,
-IaI
El1.IIi
* El
I k
I '-'.9 *
I' *�""�� jiV.
the Eleasser model.- Similar read5.ngs from the curves of Fig. 22 whichrepresent P(2213 cm 1) iadicate aa e.ver. geater deyiarion from th" pre-dieted1 lc
If P, is restricted to lover values, such as 100 mm Hg or leea,,Plasm- has shown that theory based on the Fleasser model predicts thatthe strong-litme appzuziiwution in accurate to t5% for absorption greaterthan approximately 20%. Insnpection of Fig. 19 show-a that there inapproximately 20% relativu difference betwvian the *-adings of the twozurves corresponding to 10 -o Hg and lUC cmHg In the region whereA(P22I0 cm- 1 ) equals appr~ximtely 220%.
On Veth- besi of theme comparisons 1-. can be ccncluled that the
absorptioIs a reni ofN dam r.tllon In tne P- and it-Iiicees0 1" tbea "natLy rretod Lby a mt-ong-line 'IDprdý"ttloz. It
meem improbable that an error in th vsue of the consatesnt-eAti a. .. 1 :cc-.bt sc~ccwt fn~- the deviation ý!-eft. obreryql -exu~lts
fromth predilcted behavior. It con be shown that it the constant inEq. (31) were in error by an such as a factor of two. the data wouldstill show deviation from the strong-lne approximtion for smaller.va~ues of i.t~hw& those predicted.
It IN of lr~terest to copare the rvsults of Figs. 19 aMd da. Whichdeal with absorption A(v) at certaln freqaelcls, with thoe* of Vig. 16wbich deals vita trital sbsorptlouijA~).(v; the curves representing sit-eorptlu.u approach a very definit, upper limilt of 10%. but the cum*representing Cotal absorption tend Wi. ln~teat a usm:1 increase witbIncreasing vLuwe of w, for even the larger eswoes, as a rts~t of theevotInnxing growth in Ehe wings ur the ba". fte curves which coneoepoedto the lowr waltwo -0 r-;--r-- to all three of tbaee fig~ase all eon-tamn portions Aich are nearly et~n~itt with elopse of aweroxmimtely0.5. 1hUs, the total atcol~l'on as Wall ea WeraR .( boilmI-crase~s *pp~r~ijeatei so U atoare s4..tU -A -orter Co4Vcntram.us for
~arai ra '_r4 values ur V and rs. l,%alar cosprieoo of Figs. 18,Lb AniIValOgesta tat tat smil~ depenienee ons 1Pa to 60 peaul
41.0ftreret for telak seU4 rptlon then for pemett aboorptlona. 2M safmas
absorption at P-nsa. amd P-mam. "evsy*ctisty.
It was suepeted *artier thet tee absorption by weak lines to thewlame or the bud UW41a be os" -7 "As NL-otrw ewcovating for %be faco.tat tme total neOrptnoa aid not show a 'q4afv-roo% aepmkuon on Pftsmoer, It to seen that the absorption at A-ma. ead P-osa., * itb tousaftected by abeorPtilna In the Wisp Ur Ust bood, OWY-4 On~ly a. O~t~tlygreater dUpesevfs* on IF, than did lstoheW) aehorptiem. It ts oweeials.thoroftve, tAftt t1-. '*ai'- -f PI.Oher 1of !uhs.j sant'ItIes. partcca at-teorptom or total ahaorPtIl.. to eshibit st-ong-ne pracprtie- It "~largely Lu UAs weak bead.~ whirb a-v z .. t%-. stroao ,6ajsxoaXl
6~0
By considering Ui.e 4tifereaC* Detveen the growth of weak lines ixidt"' gre-vt!h -17 -+--Z ~1-vi, t_ ' t:.zb '.give a IUa.LItstiv* expleartlon of the greatly different shapes of' the ab-sorption curves shovu I& too rl A-imad~ piortico of Fig. 4.
It ha-- tz ctlmm th.at the Abaoryttoa at. F-mas. and P-max. bas arather la"g dependence on Pg over f!ý,rly vide ranges of values of! v nP*. It Is therefore possible for a jumple of low absorber coacestraticaand high preamire to produce greter absorption then a oe~lo of Nickgreater absorber caw.entrtatio but low pressure. MLIo is the casm for4.h' spectra In T1g. 14; the aauple, having the smileUr value cif abagrbor
cccentrat~cm Lad hl&Mr pressure sabve gresat. absorption at *-msx andP-max. than does the samlt of larger atso:er cencermtration and lowerpressure. L),werer the I trne Im the viAgs -.f the hand are such easkermad grow -'et* "aidly vwith incrvaping pressure The .becrptlim In thesiP* at tof moeed. -,- t.trefore let* !:__- t.r meple having th * m=evalue of absorber ccaceotrati.-.., in spite of Its higher prsessre.
RMW A? CA13O! No==
A. M 2143 M-1 CD O
M14"totaW LisaUfied CO as a panomemp awpopsric 6"uesthstfrom solar tra *Wtaizod at Columbus. Oklo; sAd several Investigators,incuiad X9, hae. *Lace ~an stAdles of mwo CO Comanat la thMa4eyhwere and fO'iim a "osawturee -it seaeimatep a.1 awm om per airmass. am Lt mme is an aft"epheric Path cceeazwag tMe ems emeat erair to a vertical pott WAholqb the *&tire aumephet
I&V NOMIGeNO . bNAn Of CC !-WSa AWa Uhe V3 V3 O.a4 !~A thatinuiher.1 viMasw v~ick 11w~ betweam the stUmag 23DmýCQojhmas andthe 1"5 arl Sjtl %amd. 12e major par-Aas of tMe obeepUm Sy Inthis epoeiel regloe 10.1"e to the Nbumain* vibraUos-rq%%Uoe bendot %"e Cope tovL"S C~k . otwr isotopic bends 0ocw In *Ms, epeCtrereqhO. a.s -tý .' 41 ??a-*. ftAqd Vb-1 arw -P V0 ft aaw o atrem Umot ts . I& Ume peeeee* "". re 1!r ai. abeorPlm, bea he-Colhor awe reterred w # ast :1%i. --- cm V-tae.
k~pealmlely Ift sPectr ot tkhc UlAd we"- obheiamd In th prsseetstlSji~ Lj us:Aq tbe.-.--ba sp ~~~atelisg with addorpilom to"*sof !Mgtsw Cjý,6.i, 0"d 6m M. aiftervut Cahisotamma, of Ce awere U004 tb ProwIde WVele at aweý%&r towery,%muesm from 9.6 a 1W4thl~.6 La.. n* cm and .w preetssr-s tr~a apa.itl 3 wa 3MO w gg.
tresimme of a large womes of %bowli'e crvee are sbom I& P14..rv-4, %%re tbo appowam i grompe. So vuaime of ebeerbsr cuseemtsa-
%-Q Va NAj #AT&.s1 pres*ur P 49 Ofe Um Sme t rersP.Q.a to es
5rt I vnmmlHq
-~ZZZQJ20~ 313 !06
4025 25
a *- L 72C7'' .I. - I ~3020
lk49,9~
IIE~AKIt 3
4A.-
Fla.S~wain of lh 10
: II I ,1 I l
n • • .-
Ki
* \' N. )
" 1" 41 p
-i, -.. ..-.) •. .
4%4
_ I!;!!•! I- -. 1I!
L •'N
' ' ="• ' ... ' ' l i" i ! ii i i |- • *' ! ! I !. ..
i4
S• -• • , i ii i i i i
~~~10
Ji\
77-i E
:0 u *
00;-' . j% C' 3:
N
\Rl 10£
C\J. ccN
WrdOO N03
2I--r-
T E i
r-T---1-------] 7 r zw !ovuo
cliNOldOS3 A30
InN
o M ýU
'Ej
qU
_6I~ NU ~dd-.oC38 LN3 6
67w
LM I- ~-
20 w in
otmos cm mm Hg40 0,165 Qsi q
0.709 412P.67 1555
60
C-,
Lnm 6 I
20 Sw in in
otmos cm Ho0.349 2034 0 1, 3 1 1,6 1
5.52 3210
60
80
2300 2200 2100 2000
WAVENUMBER in cm"
Fig. 29. 3,ectr of the WJ14 am'1 CO band.
spectrum appear with each group. All the spectre. were obtained with
LM sa ~ pectroe~t~r alit width, vhih-' coruespondeil to pzroxii."Oly
All of the data for the 2143 cc 41 (O bc.d included In the presentreport are collected in Table 4. rne abaorber cocneentration v andequivalent pressure P. for each sample are shown. The value 6f theequivalent pressure P4. vas calculated from the total pressure P andthe CO partial pressure p by the aquatlon
Pe - P+ 0.02p, (32)
In acnordonane with Eq. (134) and Table 1.
Included In Table 4 are tho va1..c of total hand abeorptivuaj/)L()dvalong with the observed percent of absorption. A(2116 ca-1) and A(2168 co-corresponding In good approximation to the absorp".on mainse In the P-and P-branches of the bar!, respectively.
N~ny of the total absorption data listed in Table 14 oee plotted InFig. 30 with the total absorption presented as a function of the squlvsýlent pressure. Each curve corresponds to a given value of absorberconc~entrat-lon &An shows the affect. at increasing the total pressure by,adding X2. Curves F, 0, 1, anM I correspond to values of abeorber con-contration which occur In the seme ranhe as the values correspondingto curvies S. C, D, and I. Taama two met@ of curves represent slagpevhich were obtained by using two abeciptIon cells of quite differentlength and with quite 4ifferent values of CO zartial pressure. Rhiw"these two sets of curves represent approximtely the ese m ites ofvalues of absorber concentration I it Is possible to cosn*re the totalabsorption of a sample to the 6.3!.ca ce,.1 with that of a somple In the1400-cm cell which has the taime, or nearly the sans, values of!vsr Pa.Such comparisons can be seen to ind~inmte that tbe resulte are consistentto approximately *3%.
Ths general features of the curver of Fig. 30 are the smem as thoseof the corretsponding curves for the 2924~ call N60 band uti1eh ware shownIn Fig. 12. The variation of the total absorption vith ob~ags. in vand F become very slight for large values of!w and ?4,. This insultis iltustrated by the crwvinW of the murvom In tbe u'er rigthandcoruer, and is due to the fact What X(v)w .,> 1 for moat frequencieswithin tUP I-end, and the total absorption changes slwly.
There is a general decrease of the slope or the curves toowardshigner pressures as a result of the cheang In the shape of the spectralLinea which was described in connection with Fig. A.2. flowever, the de-oroaso h, Piore Is less pronounced for the CO curves In Fig. 5n UAanfor the 320O curves in Fig. 32; this rvoult #uan be explained by the fart
69
A, J
8 144 40,
F 262 400 8"4c4 E 132 400 -
F 09 635 - - -- -G 555 6.35 -
2 94 635 -
1 48 6.35 - -
") -ý- oý!ý-- - -- -. p
~ :44 35
1OU 55p "107C,3 155 *-
7 D 3ý0435 . ,f ,5
tj 000154 1
L~. L I±LL L L IA..1.0 40 '0 40 100 400 KMQ00CPs in mm Ho
Fig. ý0. ft tOtAl ab~owotj~o of the 4;1'J. _.M Co "*n~1Ytous *qiilvwlit pmassuzw .& 4aapgiAs bavingeoautant volmsu of ab~ozmr comeostnan
To
that the quantity 0 .n'/d 13 les3 for CO than for NpO at the sampressure. By using an average value of c . ' 1.8 cm"I and a - 0.08 cm"Ireported by Sbavw
9 a- a P, of 760 = Hg, it is easily shown that . - 1
:zraCr5pon tc "e 7ro Dr. Hg. It !! "C-nll-0that for N20, f fr ). equal to approximately bWO - Hg. The dapen(2-ence of total abanrptlo. oa Fe therefore stata decreasing at a smallervalue of Pe for the N;, band than for the CO band. Therefore thi structureof the u band wvoud be Leso "amearc '" than Lliat u. the N2 0 band at Lhemd-sun va.lues of Pe used in the present studj.
Several of the curves of V.g. 30 contain portion. which are nearlystrallht and parlle/e +,, •ch other. The slope of the straight vOrtionsuf these curves is approximately 0.4. This result indicates that thetotal absorption is iro;ortinnal to r,'). for amples whose vnlu-c ofPe and v are within the range repreeented by the etraight portions ofthe curves.
In Fij. 31 are three curves relating the total absorption to theequivalent pressure. The curves of' Yig. 31 art different from thoseof Fig. 30 in that those in ?IS. 31 do not correspond to constant valuesoe absorber euacntration. ?be curves of Fig. ý1 correspond to &a&pesof CO alone In the abeorp~ion cell, and the absorber concentration v Istherefore proportional to Pe.
fte features of Fig. 31 are sladlar to the correspondang Fig. 13for the 2224 cm- 1 32O band. There is a decrease in the slope of curveA at l.ow preaszes ae a resu~lt of Duvyy1r brm&-si~a'g, &-A at largevalues f v an P. as abesoption Weme nearly complete. ths curvesof Fig. 51have straight porti'v.- with a slope of appmswintely 0.90.For values of v &ad Pe rep.-se-*-i by the stralgt portito of thecumes, the tolal abeorpt.o-, to therefore proportional to V?* wherea * a - .A.~ V. li p irualy"Q La tht41c irii offg.)%ht the total abeorpit0o, was proportional to ?Fe ,. aroforo a O.and a - 0.98 -O..6 -... It it acetoiagly to be eqected that thetots; acsuu•yplu Is proportional t4o 0 P'. This result Is coo-firme below In the discuss! )a of FI. •3, where the romps of valuseof v an re for whien uhis simple relationship is %a&Ud will be deotr•im•d.
In order to determine %be deleadev uf total ab•orp•to• oon, ab-sorber coaoeatratloa, w, valus were t&an fros Fig. 3A and 31 mA plottedin Fit. 52, In which each curm corresponds to a coaataut value of etuiwa-lent pr]eeurs l"advtcated in order fro tar to botom.
le lower port•ie of the uppermuet curve, hchb ,vireespoAde •aequivalent pressure of 300C ma 5, ts liemr with a slop* of epprm iy1. P•a• this portion of the curve it to 1yoslebla to detrmiem directlythe value or u busad iatensitylJk(Y)v in the zam anner as am#onrot the 222h cm-L 20 bana.
71
ý -TT r- -- I IT I-7
0~09oLL0~
til II0c
U ;1-U ~ 010o) V
7
-410-j,1
-A
�1
9'I
I- .4-\ \ \ 4'
\\ j4� -� E
C 40
z
VFK -4V *1�
I. -{ i..
F
L-4 -4
The value deteaired for the ."'3 cam- 10 band Is
fk(v)dv . 260 gtso-l M,-2 , (3)
This value, whleb Is believed to¢ be accurate to within *1,4, canbe c de~ to the V51ut Of 23", atios-1en-c2 meortedi by Penner AndVebeg1 , and apparently not corrected to 5S. If the valuea of v InF17. 32 bad mot. been corrected to ot&Adard temperature, a value o?
)Iw. 2.5 atmo- 1 ca-2 would have been obtained. ath dlffervnc. be-
tveen tbhis alue aod that of Penner and Weber is vIthin the limits ofemperimenta~l error.
From the curm of Fig. 5P It Is possible to determine the tctalabsorpticn of a-~ esawie whoib* vsiuee or avortoir toneentratico snequitaient Mreaeure faLL vltz t.h !eomp covered. cuwever, it Is pooel-vie to derive empirical equatium which relate total abeorption to the'rxmete v and Pt &Md make it poesible to estimate total ab-orptilowitbout te 4ue of V'e curves of F"1. 32.
Itie curves u.' Fig. 3Q ceornsr at the lowst sand higeat values oft bUt te fvee lower e;rvae are mearly Uwaer ad parallel over a wide
remp of w mar the ceanter of ta turvet. The slope of the ilimar W-rtiot. of te eawr-e to ap mlmtely 0.;; thus itdleetlag that thetotal eaborption to proportional to v
0 .. %ae rno or vlme of w
ammi t o for *Ic JIA(v)dv Is praporuoal to vw'55 10 aPTO LmtuAY theeme the reap for iebA (ve was found to U propn'tIonal toPev' .In the i0oi"etoe o"IPt|:.,1Z5 1 4 sup m e4e that the tIabemrptise we Propwtie"ei to 40 . ". 1. I wme of the eqomwatof w %loe ware derived trA to 4Lfferesat sets of eurvae ar emehom eet4 aile the llUmte of e*mp mmeal error. U auvee of flu. 51 eorteepon i0e17 to 0amle f " mt solam, ltle t" curvee of PFi. •2 are based Oneempi*e of CO slam as well as ewple of CO eased with 52.
Same. ft QVI %&Ine• ajLue of I and Peo the total absorptime io pro-portional to vO0 55 P*O.hl - (vp.O.U)O.55, it s of tlatsmet to ImmeU.
lthe MW of alue of V *& te fts rarb hW tiota! abeorptionuIMt 13 e*xprevss4 to a khsaa4".n of v?, .* in 2der to chcIL ts poalsi-blutty of "uSaa oeub a fteatlon W14 to Illustrate he 4evitlow of t0edeta trm It, tbe twvs of Te * :.;. t Plu•ttes with ti toal abseorlticst -4iknt the variiblA '& 0 n8. Saul ;oa we vorteposim to a givesvalue of Pe U imiloated. The polate 82k ,m to net •r•.'t:ten etmal;aa.&es b..t norreepoud %v values Oz- from thv .-mrvee of Fi~p. 5*) and 31.
It the total abeorptioe were a f.uwtloa -f the prod;ct wP0 0.8 forallvaldmel eof vc A ',, the ws e. of Fie. 53 eot 14 aWlloao. ,b. ItIs sewo that tiere to a %sther witle region over *tlpb the .urves zor'v-.spoeding to Pt :5 21.- maR am gaý-ly eol*-Ownt. PINw #%0 jut-wa *tis emy to hbow that
7,,
- -i - -
-!
1*1
�OoO��oO 1U
N 2 �0.
14R
\ N� II.. 0
N
\ 1�9.
.iY� 33
I
-1-
��KK:\�'.�'. \ I
.4
I1.
\\\ I.
jo fA(Wv -v 2.75 ulG.)055
e~~for
10 < (~l < 40 m-- if 20(? < ,<760m K.
In the lower left-hazi jortlon of -rig. 35 the curves corremp-idiato higb pressures fell to the right of tbz .. r..... corresponding to lowerpressum-es. 7his rec'~it is eoaeistent vith the results of th crvpdýsg ?IS. 15 for the 320 bmAM oid Indicates that a function of pgive. too awwb weight to the equivalent pressure. Tht date correspondingt~n *he ett-rr Ina the lover Witt portion =f tkw figure could thiereforebe more acum~luay rep see-te4 by a funortios of *PF4 where a !aI"@s. than0.8. In the uapor right portion of Fig. 33 the curves eoryespoadiag tohigh pressures fell to the le-ft of, or above, the curvs eormepomiilmgto low preessmas.. Sam of the cur-va ý.oz-msposdine to lower pressuresto not *zteni to the rilpt-caa portina of' the ftguie; bowever, it is&"&mart that Ir they vare .extrapolated they woUfldil below the curvescorroopoediag to bigber pressurve. INe dAta represented by the rt&%t-hamd postion of 40 figurv could %am@ be move accurately rpie..oted b7
* %-tifml -f v 0 .- w %e !q *' Wtrn t~w- 0'.4
th4e U total absolVtion mma be reprOe..ted by a faatm~ a,VFQ ve-cvrW* alm ato of % ad P , but suma a zImuce gives, We
*A"a 0eig1t to P, for Gov,. awa SA ar Up .ai6i1. r* T.~ " mu ,eiiuof v. P~v Iarpr valms of w sheb a fnctIon gives tm little weight%a %. Me latter result v*%Uj be evrt-'tv4 as Me heato ofth %M m%ulalemt: ftr the etroeidme .proxImtise *kIeh giwe the btefl alh.O"PtiOS as e ftnoeea of t% tamll to 'aUd for larp ! Wan eml ?,,.
In Grdar to eoW the relatiomup be moe t"0 tetel 0aiwarum OMate vFArIejl* VF,. these parematere wem toeii P.1g. 34 for the Alt-faseet winose of the preesure Indioestsm. Ovr the w~or Vortem ofP&G. 3h the uaw'e 4ormspomlag to high preoser. Li to %ariot at%Wture caaveeesrebaskieg to tWer preeaWe. Ttis rwelt Is, of eouee,to be OeW'-'* On %he %**ls of Pig. 53. lowewr, Is the *"r P40ht-hame W~vtiae of p4 !k tho --- Me ~40M. on w., 1h0 tjrVee cot-mopm~lo to tUm Lear pyaeeures, 20, hO, *Ad 100 m 31& 6e wt eft.MAa* ftr to tI* ow~ do %b te carset "onwpasikemg t0 th hlwr pm-sSmzs. 2herefore, oe"m oianly OSUMI*t ~ve the %"wnpremmee -revwoul owtur elative to the high-pesez eam wns In the rjght-heal per-ties of the fIg-ar, but 11 wVMAd ftpr t"at Iith 00ue~-pr~s~urs, mWiVGA's ecve~a ,te oiali "Or~y COawe.-0 Il w et atob-pfteeuW
MT"rve.
Co"It'tt z~aspist of the curveis toIg. 3Ph vbud Immliestvl~dity of the etrameg-lim eppv.uinlem. On the %malt of Us surin
e~r1inuoU~ynh'AI-WA. iý 1a e #,Awim4t that %be etreeg-Usoe.-cjif¶.~ cto~ ýtt ' a.11t tf v t: !A.p *-% tr
of 'be b..1 is warty -vv-t end Ohe epmleare of toftl Opeorytieeem both 1. and P, to amall.
TI;
TTTT -
� ' '��\
�\ \�
\.
A �'
\\\
N
'B
B'
\ B.
If cna in willin t~o allow a enu.eb as 110,-15% error, tt In poserbl.to derive from this zw-vo of Fig. 4 som rq~tkwr simpo oqu&tooa *t ibrelarA vua abacmj~on ;. --* variable v?, to' valuea.; cf fAkv,4v ..oincluded by 1q. fi) Th. empirical equ&atimoa which have beta derived,said the regon of validity for each t Iasa tn~loe:
for
an o f~vd (120 cm-1 ,
20 F P < ?6C OR le. (5
and ~ ~ 10 < fA~vM. < AU ca,.5i3.(6
IL 16 000beled that %Me total "SCOrptie of a Adwa OWO earbe datvmuimd marv aecezh141 from the euwwe at P14. 32 %thea fthesapdrteal equations whieb are t.e ,&e M. tat It migt be jeajh1* Wasks deewt itheast ihe uem Cf th0 ouaxw. Us a~ria~i fs.(M.), (3s), and f16) an soen to be vmestl dor n~w via, I%*@ atvalmem of 0 WAPa arni theY *I* loolimi to give valved offAL V)i.be-Purkto to' Vitusa *1% *=Opt for values of W na 1P. &dr Qýlirnitof the reogto of ve4Ie1ty Ave JFA(v.w gtve bM te qeaUw my to1* eswr *y as sock as W4~.
It 1s "1 i t~aft- ft. (35) asi (3b) bamw the 1-i eqn:t444 ~astbeaul of a troag~'1m awroximUer, I.e., tme lot bm~aeery'm toeat~mctrc4 of Uma pweiemt %*, baor, neilthereof tboe *"aU* owAt. (VOm cer"OPeapon to taw &%Mat-rat reiAlM. whlob .heel4 &AZ110 the .04814a t&Aa Of the OtWA-Ug Sppoe~ifd.~t VIVA M everl&W*of -f epettral Uwe. Fort ,. *ra -ve S tiMU ¶b0 tot
Usth Saaaw.ltlvj of VAPO O.t*a,,rvt relation i9vee to ,% ft~wseeemS.at ath $30 bude *1"o 40104 to the C0 tam.
Ihe atcreyiemv at A-M.a. .mA P-mas. boe ban. iaveet~ga14 to esomo duda We to tha sp* sed W44 PAT ~ th 1Vb . To voloa atofeerms4 e&seeetier AW14 to-a ~ at R-mat. tee a 0%3*e portlei of theoe"ttra ane plfpU.*& to P4. agate~t the eqkkvsqulfat pruegam. ~batuere Mrsmre eet a gloea VOW of eheelr" conomtmua m "m Imeea'ad.It to MOta *hA¶ aeveral Sr MW oertea bow* Pomotau WWA are Owas'str%701' W19A s4Ps equal Wat r epwunmtax * ,&* tonesmU. t~st the
LI' ' I7 0 n. 0 cr0
\\..
4w-
\\ <K1 • &.
-' m I
absorption is propcrtiona~l. to P. which Is nearly equal to the keO'*5dependence assr~otnted wlý the r 'sare-rccl appro-dnstion. "110 otde-features of the curres of Fig. 55 are siu±L5.i to thiose of Pigs. If and2C vhich vere describtd pre,.,!-u:y.
Vna.ucc of p~ercent ab~tnr4 - w.re taken f.-ou the curvet' of I± . jl5and plotted in w~ig. 36 with tnke vtriable v?, as the abaecona. E~achcurve represents a given etlue of equivt.,ent pressure, and validity ofthe strori-line approstration would be Ullustrated by a coincidence ofthe dift.,reint curvea. Fw~Lions of sow. of the curve* were omitted frnmule figure to avnid overcrovding; hbveer, points were Included wbichladicate vhere the ýurvrs vou.1d nccur if they bad N-P.eu In.,luded. ItIs noted that the 71ui ujppe. ctirres c.vrrespoiLlug to the lower pressura.are ne(srly coPnelden't eovvr a 41vd *Airu- of* values of the variable vP,These Youar curv-es also contain portions which )are nearly straig*bl. with
a aopc c.' apr.:i-j&&t*1y~ 0.ý. limd uaing at '4*~-2ejendencs.
The r~oults of these asasureaatot c.an be zomparv-1 Lu Lis absorptiontnjat Z'-max. in ZTik. T- 4*r lvý.Lov_ Lhe valuwe of A(i6 ~.s 1 )
against equivalent pressure P,, where each t.%Arve represents a gIvwenvalue ozr absorber eua,centration. ?be gross features of tho miva ..fFijA. 3', are. of course, slimiL to thi~ae of~ F#.~. ý5 which represent theabsorption itt R-wv 7-h. vtfig~l. ;':trtccz -f I=c t. of F1j. 3-1Witave. of appr' xmt*4 0,45, whieb to ait~htty loes thas the valas
Vailwo were takes ttvs Pig. 3T wa plotted In Pill. 38 with We athe abscissa. For the !.Arpo# values of 0P tas, cunes !oattrgs Lanappoach IWOO obsorptioo. The stnti~t oertion of the cu~r-w bave aslope of approximately 0.'2 as nroqx* vwa 0.51 for the eua~s cf715. 36.
7%aws t or cerawata values of v MaW Pe, the abeorp~ioe at P-MR. OWifl-m&i. for the 21h3 ca-' ýU hand ihave r 4opb.Unce as tbooe parmterswbieb io oaly sUebtly dilfferent 01- the 0 alwarl.t~t dweadwe forwhieu the absorptloa 1w prercpor wl~ to v *. AsIn the ease ofthe obeorvttom at P-max. cad P-max. of the P7'4 -1t 10;O %ead. the max-W-- deef~ 06Fet sowht Ises& the 1.)'l Ispemiwem aseoelat*4with the square-root aptantlsomm. U10iVei. the hewlatit,. frM NSs.qaare-root depeaiew. Is eowt~orably Ise* tar the <.0 buma the&artthe OZ- %4Aa. IL wes pointe ouat In the tiecawslou of the %O lbabd 1?etthe absence of ak 4queyw-vokt Aepeadea:*c a pressure eould be attrilwatedto the weak Also$ %etch C-u: aLlon wit,"~ %be, qtmrýg 21m of the etriwotu-moomot.! tax.r. It 12 svlli katwa frZ Usb h igheolutloa spactr% 41w-.#Aere are fewer eAn Lives la the COj 44w., than is the UpCo bamd. it tstherstore -0.9 #e,6'rl Stt. *hat tIM de,1.'olo At the IM0 1LsoVtsq* t irvitse #,ttre-raoot depouiew is 1.50 tbfti- for ths Xv, .ateorptiou
It Is Nrths.- '.-.AA. "- leaciw L4 4*4LI U tbe Sq&Mw-rvn% 4Ared-em.-* of the soaV.Crp . t ?-omn. to orestor teas at A-mos. for tho M~ bend.
so
¶ C
a tI"
N[C &
I;a
IA
.4
4 . � a
.4
- I.- a
.4
L I,
.4
4.,
. 4 1.4 1
4 .. - I..
4 I
i �
~ '~ .J 0 (L 0
CIOaW\' II
006,e1T*N-cj ooo O0*-j4\~. \\v C)* 6B0xviZ&
A A-A LA*-
ooesdt ,uig
Al.though Ae dtifference in dependence on Pe ic small (PeC,45 comparedwithP, 0 -4'3), it is belic!Yed to be significant. Further e,1ilent.t .the difference ..a. te ia~en by !onyaeing the straight portiors clý tnfour' upper curves or Fig. 36 with the corresponding curves of Irig. 38.The currd o~f 14iC. 56 cr~cur ':onsiderptbliy *'!osrr ýngether than do thoseof rig. 31J; the difference in apacing izi.Uý,aves that the strong-li.wapproxim~tinn 14 ur mweearly vulid for P.-mx. than for F-max. This re-sult can undoubtedly be' excplAined by the preten"e of rather prominntlines of the isotopic ban4 Cl,- tý-'G roar P-imx.; the lines of this Isotapicband are much weaker near R-m~z. and therefore give rise to loses deva-tion fr. tche square ron'. Ilnd~.. ia difference In the relat~iveota~ongthe of U~iy' .xo line" in the t.wo diffexvnt, spectral intervasj~is well known from nigh- resaluri1on spectra and is a result of the shiftof the ban'i Center or the -713 A~16 tAnA relative to tbP center of thebend of the more 'eon let.
Cmr.Mnson of the &,xaight pro.Utozu of the four %Mnr curves ofFia. 34, whlua- reýAO~sfA(v)dv to0 vP*, with the corresponding curves ofTIe.d 36~ jnd r. %!go ird~catee that t~ c;-=rs root &approxmton 1smor* vallia for the absorption at P-max. and P-mi. than for the totalaboorption. This result eta undoubtedlXy be explained by the Ntet thata.0 west iuoze war Lao vinre of the harmi ecotrIbut. to the t'.tat ab-
sorption bu, noc to the abooryl-Ic:. at P-umx. sad P-max.
A. Tim 49 cc 1, CO &MI
?toe CC overtons band at. k260 co-1 was Iflwqstl~mlie by tal*4 alouiblO-pas. mfleo-bee. Modo. 99 Pvta-9ianor spectbometer Ath a U.?
&t A. A dent.. glowr serwi as U*h soyasce &aA a fthermoetul ast hedetector. latereel "Jx~aoov tnhe iaultjile-travereal rell wIebweas s~i. m.,4 It possible 1, record spectro ut each suol* ot Is, 6, A6eel !:? treeq-VAle ; ~o&s~~ ,. 0th lesgabs Of 6P!, 1232, 2"5, U&
emca reepectively. Tbo sprctre veae replotted an a Liner seal. ofpoereat &Wbeorptiod ornwe vwesumbr, and the totl abeorytioa wee do-toeiloo ftew *A* r wimdr *eb spoc tm.
cý%ýv to gqvwral.*v tke ."llotted spettra arg ohmv in M&P.39 and hfl the Spectral .119.44th of the espoetrinte' vee beotwe. L5WAn 20 ca. "
TAW&e h lit*I the aheorrt1u" Praew~e .4 OWe toahl albsrorUemNt V-1 *ýf *be O.ra..'.* Otta.&n4. T"e "nl wee at wqf tamonatur, ft1ehvaied by apraIsletol) 0C dunlog the voitroo of the eqeimse..
Is order to 4setrmln the nime of Pa for oach swol. It wees irst,weessary to delewtime the welie a tse eelfVromsdog emfiseiet Iin 9j 1, lk . C' . e the ebe. %nWI wer * for WIe pertue of' the str*was mot a 4bl-b.tyelastiwiet, It ,14 sar p~xeablo toasevl%Ue Th.e 4f 3 t~y the vab4 4ee0aiI.e4 p..I%%f.Lj N.4. 1,6 22a. =' Iarcam al5 eel COI heels. The motbol o# Wonriamled 2 fr this heal mbd
[ b�; 1.-1.�I 2F U
Ir - -I-
I -�
'aa
-.
q.
I -.h.I - ic
40 p-- 1 e
IU 54 mm 42177
80* ~40472ainm cm cm
424 0di I6
'1 mg
75656"
4KX 4m~ 4300 4100 4M0 4300
WAVENUMBER i
I*'- :o - 0 af
I' I -- T 1rT
C -
a �E �*7!�- 0
C,
9)r�v a
1/7
11-7 K. P
(I C
-A-- �..A.
I �I,
'V Jp
0
k
A
4 N
'a 1K-C
I�C4 .�iE�M3d
use of the fact that several different samples which were stedled a2co-tairnd approximtely thp saw absorber f-Amentration at difforeoL ai~hloogtba. For emmpl , an abeorbor concentration of approximtely l14elmceanm wa obtalsed with path longths or 625, 1232, sand 2445 = byusing hltferwat parital pressures of CO in the absorption call. pmectraor tomb or the.. samples were eltaine4 at Airffrent Values or totalpressure vtich war. produced by ading 1,,. rasifferent samples, whlchcoutslne the oms absorber ecseentrallo~ but dltfoeset partial. pressuare*of CO, aweesaftly required41trfereat amon~ts of 52 In order to producethsae total absorption. By compring the diftereat Talmo* at COir'dtal preesam mod %p partial pressure required to produce tShatolal absorption by samples havIin the same absorber conentration.. Itone possible to determne the Volvo of 3 accoarding to sq. (13). Apprewi.mately 20 smepwoto ~aleulatlone, which involved a large portion of thedata Otained for the 4260 M..1 CO bond, Wiws mad. lheft coloulatlornviC*iqi & Walum uf 2 - lia 1.00 UI Isb6lUe. "a"6rA166 W A. ZMs
aeoordirne with Eq. '%lk) the Volvo of P, van doetralmot by
P, P * 0.0 o 16 , 07r)
Awere P ts the total prssurew and p to the 1partial proessur oft C.
MW Volvo of P - L.kA.t0 sawwat larger twoe the win of L.ORbbantendd for Ults foommtal C0 ft". So twoe vale differ ty ollbtlyames them the wm.lnim emprimostal ormij bovower, It wcaiA mo et cr-Pristat to nai m elpifeant ditfereaseo toa r oe -wItrorit heoal ot t"*
emp mISS 100 ValittIw %mm ff*Nvt XU the 2M 40- r20 OWi Use214) WIl 0 WA~S. Tom uethd neel to determin te Wmius or B for tUs&Mj ar CC bugl dIA ,*%t We It poealble tU S ~elct moal vaer~soi atI vwat~ the heel.
TU &% for US NJ sm CO'.40 v-w an abov toig. 41 With totaebserptlest platted as a NOWetM or e mivami prowers. "e tep eelbotest eW-wo ryposeee *login miness of ehewoer weeseetraoIcm. loseof the $"r ~WIMS OerMVsPW4 to ma &prWWicmhelv eem t Volvo OfGbhesetr 000MstMUOScm %M wines ISOdleat at. te )ert Of *&A QUtelielte the soinvei cOd Woain Talmo of ab-oier OsmsivnVtivem sayfosemlod by that evrwo. Z a a eamplaea e iae t CC alo., ~lit theWe terprseest evowes tomee4i of both 00 and %.
71gwv 4 hIvieates the sems parametaers ofe CA$ie. )0 ?or astwmwoo 00 heavl. loemer. Fig. hl Gate not re,pmeut sarly as VIM a
rsofo valvuas f1 w and P. a& 6a" ?Is. tO. Tbarefors. em of thedefimite fattiesi o? 71;. $0 are mot, peeftt Is Pig. %I# robh a& V do-eroes is slops at smal Vale" of i* A4 a 'eamit at D"Plar Vr~mgwsaml at large Values :r P, to? a ."*of Ousrlaptas %. te poetra)Usnes. Bw croUx~g or wa. CuW'M LL '.U W~r ri#%t-wAl S*Fnr at.e
mi nt c ru ia ?1*. *. ws o iseth larpei vwAliss e? w and Fe wate not
,I f I T
A~ 14Cijc
, , !.-, .-- 3
417., ' ' "
"" @
- ,4•i4; 04,
aji I l i l4
su-Iticient'l.y la~e to pi-cl... 'cupeta absorption over the banii.
In oý-or to $now the depevAd*ofe UttAal absorption on v, valumswere taken from the c.-A-ies of Fig. 41l and plottad In rig. Lh2 er thefour different values of Pe indleatedl. !his flgu%'e Is saimll.r to Fig.32, vt.Ach was drsvn for the fuu4asut~A! 0 Imuml. bA as in w.e case ofFig. 41, this figure does wiit cuoLaiza all of the features cot Fig. 32because' of the ir,~e smaler range of va.Lues of d and Pe wt~ amrereseated.
by CURjarIng b then' %-iD.2 Fig. 4.? witb the curves of Fig. 32. itVas fowiM that at a Ciiye equivalent pressure gUe total abourptIoe ofthe 21165 ez-1 band was wery nearly the &m as the total. azoerptionofaLIM 426 = ' -a-1 at the 3411 equivaenet pressure but with the valu-of absorter conenetratioa 150 times as ariat. In fact, each of tk*eturnes or mc. L-ý was &mvn by tractmg th* .arvo .%f r1.. %?ilg to the uam value of P, but with tbe va7~.. of V diftferat bly a ftet-.:orit% 1z~ to isaote thet tUm *qerimatAl ;*lamte1 nt icely the true"curves. Tiii 4- Vi'~ct tmaclagnfe or*- :.I. Witt the veius Qi the et..ciaeadifferent by a coustant factor mae poextbIs, of course, because of the
correpands tt an equlwea.est pressure of 90 m U4 WA 60% true"a Ergs?I#. 32, as vere the other three :uveo, eiewe Fig. N2 dm o~sat containa carve cetmepoalslas to Wei &Modare- The curve corysPoendin to,to m 1a Fin 1. %.I Vas Uthetore dirawn MAe aa*Lhar s1ImIe. 961%-beowwer'*tm to 50 m 14 for tbe 211k) cm-- band but Is set Iselns4* IstWe report.
!*. 'ob-*al absorytl..a of' She 620 orI %W"d for eeiomeeo to the'Usmer moor* W4 I uot be* eAmundmi trn theermse of Pig. 4*I"- the laufmat V%'WV of P, 9Von W.ot wm~e'e-tty !.Arf. mar Was U-0eemallst "aIV* *t V Ouff..~teay smiU. 3Swevr, PPN am *#bar&,Ift oelim.~4the 'At* lZU.eorytlas of both bande s thet~ Uier vlogt'amd ir.,omm thi' tz2, lu...is .. @, %(Y)4v ior the rwometai bwn woo,4.xm1' 00.' *twoe taxt of the Owmrte M4n. Ibe 4-a shnrImi
f~ Z.1-1 ' tb* Lrmr retias I* t~herefore thsa as tut of
of~ 4,v, wloltt lmo Mý%-~ I ra Ajffytrlrneg.%* af valuves andF..q 4@ the V.MAe akrV OLIhler wthu rtotft to iUVW sha. Ills
spmo1;. aS rulakUV% *.v i reu.i*' %vl'Pke Uhe bA., it is probably!L% t"% MW lot&,o bom~Lviono U* the sst owencee bar ýf Ibe 44.terejtwe I'r' 114.' t. 5.. whftl 4'I. with tMe taw~maiabOTA .~ W7 *%n Vr P ., ami % 'MaIve nf 0 vktith I1*!l* WeretU!L 4- 'te f-6104* IhOU' wla- 10"Orti.uO it 1 eWW4 Lssn& imt&.".
Q) ~S) ad %)Call i FVbaftV.J %Lsi & an :t& ote f~taeod'1vw by
cl-c
I I I- I A.-
ol0 o CM~bo
It Ma been iz~trwn fro qu~a "z n'jt "re no 020 cz5u in ratwer
Mrge quxntitlefu In the attaospaeren &. Me planeta Ju 4 fter, Saturn,,
to be a permanent zcnutltunnt~ of the eartbn atai~sjhere; the aweraw
Ly VJi.LMW.
A;;roximaaely 1';0 absirpvi ..z.ntrm of C14 were obtained V~ thespectral region from 3400 - 100 ra-L. AbsorgLi pai l:-~ength.s of 6.55,00p and WfOO o wevre used to obtain v"lIzrs or at~serler encntantinnfrcG 0.015 to 188 ttmos cz. Vn~ues oftta p, 1Iressure were wi?~el frf-capproximately 5 tn 3000 =m JtI
VAL'iwal.j '&~ wA the~ %Lv...VjJL1 'JccU. in two Alffertat WervaLs,
one between 14.00 W-. MA( ̂T-1, W the o~ther betweer- 17tf s.=1 11%' cQ.?Ratings of many of thr Aparvr of' Ith hlgh-freq~er:y region are pre-mented in Flea. 434 and spectfs. of the low frequency region ares hownIn Fis 47-51. Portions of som or the spectra were asitted from the
portions ur sun of the absorpt~ion curves for overlapping hboorptioafby My~ and HpO, which occurred an Impurities In the CII, and In the airIn the optfna'aLh of.. , the nlwie..mLe-tr. For same of the maz;f.a eon-taizaing very large value; of absorber concentratl. Me 10 saoextended Into the region of the 23502 cz- C02 bsaJ, ^xi Wwa.&me of theCOp) Ismurity In the CH4 it van necenstary to correct for _^O.. absoryptioobetween 24.50 and 2200 co-&i. t was alin necessary to corret. Or sapWiom@H20 absorption in the region between 1750 and 1500) ca1 for samples oflarge v. The effective slit width varied throughout each absorptioncurve 'with an nvernGr vilue of approxicstey 15 call in the blgh-freqiuenereglon and 10 an' in the lov-rrequeny region.
For purposes of analysis the 1150 - 1100 co- 1 reglon wasM einto 2 regionp rnt 1nj5 ca-1 . W~ !Kdentificatlen ;urposes the z.igh-frequenct, reglon In referred 0o aa the 1550 ca-1 IMn and the Ow-SomwipwY.t~Ion as th.o 1104 es1 L.ao?? ahaagevee W.. frequencies ccrreslQod VaWo canluev.of Weh tvo stronger onnam in rtnc region. 811IL~ayi tot speft-tral region from 5haO0 - PPV na-1 In mwfrorr& to as th ýe Co c.'I band.Since the rzgiou referred to as th~e 15.50 ca-1 bane' oKs In the regiomof the water vapor ahvorp~tr., the accuracy of the traced speata %101the valupo nrjrA(v14W O.r this AnM are somewhat leca WaA A, L~e otherbands.
Wfi. E914 4ta corrected for spurious absorptina ore glven in Able~ wic~ O~i~dd5 a1~a rfATsiv Mr all Mhet. bands for the Itatad
values of !v and P . I"e value of the PeLf-brvedezing -c*M-t'ea% lR tifound to be 1.!.0 Trthe 300 aQL band and 1.30 for the 110b co-I bead. Iwas W~tpossible to obtain an anc-uenim measuremnet of B for tum 1550 cm-L
Best Availcable Copy
It hAs been knoun for quid4 Re--e t~ime to-tt CiE, oc:urn in rather1:.rge quwentities in the atmospheres of the planets Jupitir, Saturn,Uranua, rnd Neptune. Not until 198 vws CH4, d:.;vered by MgiFteGt2f"to be a permanent conati-uent of the earth'n ataosaplere; the averagesbundanc IM-o tince teen Moaiid U, .t *pproxirattly 1.6; pnrtU per aLz]|r,;zby bUmF.
Approximately 150 abnorpti,)n .jeutra of C&;, were obtained In theopectral region from 3400 - 700 cm- 1 . Absorptirn path '.engths 'f 6.35,4U0, and i600 cm vv-re used to ob*'A.n vp!lues of absorber cone#nt-.atIrmfrom 0.015 to 188 atos cz. Vr..ues of total pressure were varied fr=approximately 5 tn .200"J = fig.
' •al � Ue late ;.rpjn occurs in two different. t•tervalt,one between 4O00 and 'P0O om-l, nnA ths Atber between a7)end -10A "1rncingo of many of th, •-•-.r nf thp high-frequency region are pre-sented in Figs. 4-146 and spectra of the low frequency region are shownin PSId. 47-51. Portions of some or the spectra vere omitted frm the
.!i LWh .C. '.. .... .- 4 V.
portions of suep of the absorption curves for overlapping absorptio-by CO. and HpO, which occurred as impurities in the CM and in the airIn the opt1,'al pat.. .'Pf the n.j*ctrc•ter. For soe af the sample. con-taining very la•ge valuec of absorber concentration, the CU absorjtlonextended into the region of the 2350 ca-! C0 2 ban., anmt bec"ue of theC0 2 impurity in the CHh it van necessary to correct for C02 absorptionbetween 2450 and 2200 ca-l. It was alOn necessary to correct 'or sp•rious
120 absorption In the region between 1750 and 1500 cm-1 for samples oflarge v. The effective slit width varied throughout each absorptioncurve vith an avemrSe vmlue of eppro:.-mately 25 cm-l In the high-frequeneyregion and 10 c•m' In the low-frequency region.
For purposes of analysis the 1750 - 1100 car"1 region was d.videdinto 2 regionp f"f 15••, cm"1 . For 1ldentification purposes the Uigh-freqwu;;y region is referred to as the 1550 cm-1 band and the lcx-fre•qncyS"ton as t..e 1,06 cm"1 *'6 : ai-iv. Luene I.wu frequencies correspoOd toWe cauteZ- of &he two v-ronger bann in the reglon. Bisiiarly ut spec-tral region from 5.100 - POY) na-, In r•wt•rred to as the 0ceo cw"1 buad.Since the r=gon referrm! to as the 1r5O cm-I band occurs in %be reaganof the vater vapor ab,"orption, the accuracy of the traaed spectra %ndthe values ntfA(Y)4Y fqr -hise band are somevhat leas th&n =...* the otherbands.
1h"v MI, data corrected ror spurious absorption are given In Table1, which Includes valueo of fA(v.hlv for all tlhree bands for the 11tadvalues of v and Pe. The value of the srtf-broedeaing "oeI-',nt P wafound to be 1.50 for the . - band and 1.38 for the 110b c- band. Itwas rhot.posslble to obtain an nr,:,uanL" Peasurempnt of B for tbe 1550 c€-1
91
Best Available Copy
w T I0 IT2 otmos cm " atmos V "
4 r ýbnrmH g _ UPeilmm HgH4 2.6 ] H4.6
281 25.7
3065 1 3075
Qý 2w - 0.2 w aO.0?3Satmos cm atmos cm
SI r.H. f p42,7
- 129 180H4 OH4 726Oi .
n. I2 305
m-' * '2
14--
Is32, .0'0m 3020 8 2 3 2800
WAEUME 6n q.3r
Fig. ý,ettw H e4CR n
LCH4 2 CH,48 P n'n -I H'P inimm Hg
u _23.4 W. 3912 0.134 56.0 02 V 2r 35108 -4
i1 4 atmasu 2231
756 .1525
0 -F .4--SIF ,
r'. .,420-w''
U L '1-1: -L~I K L -LLL~~
0 1(n
4-4-1 3 r4 2.0
05.8
H- . / / 5.7 I/217]cm11
20 .. L LiLt I • I-
40 3 Ot a30 A IIS.. L,._.JW..._L__L_ t .,L_.LI L
3200 30M 2800 2600 32.00 NM0 2@00 2600
WAVENUMSBER in cm-'
F i4 . hik . S 1 ,e v. , o f . ; , 3 0 -, l ,3*. Ve tA
=~
-.,: 0 a~w i-if c
CCM
3 IJ
lo
.9 I
NN
0 c 0
NOilddOSOS3 1N3383d
C-
wo x C
-E ty LJ .L.. .. JL
x 16 0 C8uln~ ~ Ponv~nC
CY .- LinOIdO
Vý
0-
20k
W MlA 1mimcm mq 1,49 m~e No ~ ogoc m m.~ -
(4'J - ~ 624 -1 003 121bu (12r 41 0 34 na
C C431 -2 1C~ - 3 L40273 ~ lf
LL
1 001 LIL~-
4!
f0052 PW ~ 0134 so$ nnvk I 41
WAVENUMBERinc"
-96 c '',>-ýt Y
,0 L '"RIC
30303
I [I4 C.~
I
20~
1600ý woo 1300 *to 4A00 10 wo VC-0 '30) JA
4 4
ot"SOV N DW 3
201 21 - a. mos cm
%0. Pininm Fg
1 7.350[ 309748
3040
80-'
80
20-
4- 34,
'800 '600 c,1200
W*AIENUMeL.' in i
6w~
W- 95~ olmm cm
40 Pe in fmm Hg
69".23'F 591
2835
80
I'llI443,
2950
S00 1600 1400 1200 000
n- 3 *:m",
band because ul the . ver-lapping water vapor tbaorption; there!cre, '-he=ae value of B, 1.36, vI urz for this Lw4 &as for the nr-`_ul
Since tvo different values of B were used !a (1l&), two different valuesof Pe appear in Table 5 for each sample.
The data %onf the Cl4 absorption are prnerA~t~d in Ak manner siailarto that in vbich the 2224 co.41 20 and P143 cz-1 CO data were presented11% previous sections. N~nY Of the 3C0e(O co- 1
lata are Plotted In Fi6. 52with IA(v)dv versus P,, vhere et~ch curve corrtwponds to a constanL valusof v. The festu'rss of the curves of Fig. 52 are uimilar to th~.ae of the*.,r-respNading curvpe fr~ the 222 ci N20 ba%.i _.n Fig. 12 a" theK43 cu 1l CO band! in Fig.. 1C. Bcwov-r, two features of the curves ofrig 12 :h:,1 tz =Cud -. c m~axiumalOP of lily V- UMLbs o*
Fig. Cý? fs mprw~~taly 0.23; th-i. ind...ates that the maiu dependenceon P. is 3..~~ which is consid~iamhi ies- +i P- +k- wfl std co vbardii.It is also'uotoJ Lhat. Lhe slopes of 6we c.-rvo eorrweponding t, ,saLussor v between u.(( and 11.'& astuo-ca Incresas with increasing vjuoes ofequivalent pressure to approximately 71 am Kg.
T!. lot r"alled that the slopes of soot of the corresponding curvesfor N20 and CU were found to increase vitaI Increasing equivalen~t pressure.w ý.. anAýAwý ! u-M . flS pahews"Un was attributed Vc The ef-fee:t OIL the Dippler vtdth of the absorption Lkk*u. Howevvr, It serneueltkely thet on !ncrease in the r-'14pe to propslizes a" h164. as 75 ma fi8could be a r*3%Url of Qo uopplor vidta or %toe i[me. it steen, therefore,tlhat another e~iilanation of the increasing alqv of the curves of Pig. 52is needed. A p~rsible qualitative explana~tL.. wtIA takes Into acrouattho rather wriqu. strurture or this ban~d foltcvs.
A higb-resolutioni e.)ectra of the jt.ko cn- C2~ baM s6wu thatIt to composed of several strong lines which ocaur ta groups, each Croup
ROi.O. beaa~ y ey.rvoimately l0-L.2 :I j.:s J a.occurrIng In thesape.tru aiA manu **aim& liuse Ut.wjhv.auu%. to beau. &scept for sampls%1WL luw pressurv and very sm valtas of absorber concentration, oeaehgr'nur, of strong lines outi be treated as a siAIl liVs for purpoacs OfeastItq the absorptio~n. The bcan coulid that be opproximated by aband node. coc~iatIng ~zf an Elsasser-type than f" sI~ong linus spaced
weaker 1fnon, epnre -. ;c .*he~or Mpthetr.
i-'r rpliktvaly low pmwseurve onemI 3 P) o pet that there wo"ld tea ratosr vids izat~ of vallues of v over which the contribuation to theabv~rytion by vie atLroL4 UAns would have approxinams a square-roozlapendnce. Tht ot#!1 abscrptiuu Ly those Unes would ttererore In-create approaiintoly as the squart-rot of the equiwa)ent pressure. Onitim %1,bor .&,4. thec ofltrtbut±... -v Lbs aslci~wrtun by t~he vvik Lineswctd ilk" .ittl~e or no 4.y4.ndence ;,% ta&i ,rossuwo. At 1-v pies-torso1 a ej,)r ;,..los of the rhor~iI~ would arise from the wash A'-it*;sad the total abiorptivin or JAe band would therefors bavv little "adeni
on- ý, prerisure. !Iovevvr, 4s the pressure is In.,roase4, the reA~auso
'III
.----1* 3
I'0
U.4
0.1 .Y� �
C.-'., --. 'U� AF ��o
-
* . I* 1 C'
* �2* . 4N I� 0 1
�...* * .. A' ,.S. 8 * 2 ' -
.1' 4P�yf
�De
* �!' -C.. - C *
ýontribýAtion of the pressure-dependent strong lines would becom g.iOter;the total (Absrptior, of --he ýmn vo-Ill tZ-:refcre exhibit tho. obse.~-.ý- in-crlrasin9! -loendence on pressure.
Without investi~pting the absorptio~n In a hbir2ly resolwed bpectr=m,It vouA be I1ftijuit to prove that the a"l-m ýxplsamtioa io %slid.':,:vevr, It can be said that it In a possibl-*~ntv of r :Wpopndem-ceon p~ressure not obserived In most atsorpti-6end~s studied, ý% Is b&P.1un Pt band mraol* which is u~ilaur to the actual, band.
Values oft(A(v)dv were takisn from the carvie of Fig. 52 and plotWato Fig. 53 against absorber coacentuution w. Each curve corresponds tothe constant value of Fas t bo sow. By intarpolatltou it to rovible "rtieterikine the total absorption of a aaale of CEk having values of v SudP'e vtt'~im the range inciuaed b , the c~u -1 of Pit,. 5,). The feature; ofthe carves are sic! I.-....._ t- t '_ - 'v zrer-'nd.ng ftgr.,t fo~r tle14.U and iM bandsi. Me nearly Lizar portionts of the curves wr. found
%W a 'Pee of apr-o3dmtoly 0.55, '',Aeetlan tft% the tctal abscrp-v ro~ort~ioz.' to v0 -553 for tht dawes Of vsl-.Ac zf L- P,,?
I.- *t~h. ne~rporttoas.
"lA te:J1.tyf!kVAv was eslatialt f.- the'he .-. mcy or the ml kotersdiw4 to
the N,-' MA the bonds 1 is ý.:*Z: to-1In he ee raumatinom of tb. intem. Ity
- ~ ~"**bar he tbp"coAluoe 'be .c 9' sq
vausof V and I~te~ .abeopt~ioi-is *&*a to iacru..- . nasere... %,.at the bandA "- t ..t'.. #", Ai va 4 Im*. -U D4I ?a-. te Y4AM m N4 Cthe comspomi1@ figure. for Mhe 3kO #3d CV.~.u~oApilti the cvrv to emitter valwo of v. beejIj, . a. V'. a,arum slope of the eAtrLW1.tv ýmrtloo R 1 we *A th.*4A Wethe val.es of the amw tahane' * M or I C%~ head ~- ee~tlnW
?U1s val~w* V61", to beLoe~d %o !ý seearehe vitula 219C Leapra ~mat.1.y .2% lt. the^ U t va w~w of )60 G~a ea v rport bywelsh, 1Phebler, wAd iWvm 4.
Veirme CrfjA(v.%sv for the 1306 er 1l C14 husi see plottod eyjpF# III fts. 5h. Several of Use 4earwet ot the ?tC~w offteaim paeas
tiA q).10 of' 0.)tat-y~ 0. 13ieatU%$ a u..m oped-idea
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!'. ,?r~ the ,Vllr fr1 tnd. P .** .
")hfnifl Ph'ov tlkt their honi c-u-t~re-i arr
banni would not 1,r exertoI to m. _144 i.,r tUi 181r IA t.I~.v(;,,d therer',e -tot necewariiv expect. '.he t-. r .-, V' Ucreasing pressuret In the P~~ inktne r.
Values5 of fA'.v)Av vere ctoti',e4 rrý-5 e of Vle. 5ýo ami1
w.r.,uoa of P,ý. indicate4. Pather large uoto~oT~~e~v rftr'ý oi r% C ;pm~x~a.te~y 0.1.8, Indlcting Chat **t.&a absirvp.
tl.'n varieL. essentially as th-! square roobt or ..be a:..cer:~'titin rfr ;I valuibe of v a;A P. riepreaented.
By extrapoLtIr~.' ji~e u.-ries of Fig. 55 to s.al-er values of v, theband Intennl~y oft .., .y' ": CH!, band van found tz, t-e FIven by
7ole valum, wtd'It , to -eved to I . o~rzor by enr i154, i .approximtely I~p greattr thAn U-., e 6r. 157 fl' c;-~ 3e;zrtr
by Welsh and Sat.llford,-
The. absorption by the .306 et-I tnd overlaps the atbiorptIoa by: L*On'l2 band frrpe i ag bobrcninralta b muw
b, cLaeen the P- and Q-branebea of the vw bwAl at-CA' i,.f'. eglcd to 1 h"rievort a tb- 006 c=7
Cf !ý.j ntrqlaute * . .
ec~entlftlly *=_!T,~-.-I, *1,rý,)t4-.0 *tIS.j :rv Me v.) ban-4. *:~isIs belJ-svnd to bo, t:- 1. 1. -. r .- lufl py .- beali n th& re4I=vhirer *.b bend&q :-.ver- i. r.:'.':' ... *, - !"vflLzei: of absorber r!- ec.-:nl Ti vtdrth nm ;- 5OrL- ' 2 - .. t,)f ' he curves frnm w' Ei th, r-and In.,n&Pty van A..*%CmLrx:
Me dat^ Oo~r t' ,s **u-l (.', NMIi a?? p13tte 10 Pg.t. ThO
vn.Lues of v inV-t, . .nx'-i v~ ere tattri frm -"t tuve t.N rtailn the jwr-v inL rilil.-anr4 portion of the !!-re Aa ztatelproviously, tte dat %or t.!i~ m~n*I we~rv LIa1'.Od Ij o=Vz.ove bhvtxi4 larg*vonl's or '.hn'rte ut .itrtii.-t, nruA tuo! ,in *. t., vpte'ir Va.lemin accurate t ifr. 9-' t-vnln 'i1w .. i. ti.!: o%,r~aj~p rtifcn by winter vnp, lh-. c.-vev' nf' F:.'.'. Y/ nt-~ )IIve'y a L t.tj'yL mr ,nl,:.,e &l Lu1 #P,-PJPtl--.'! -r'attr than 4,64 V:. tý.Cevrzr fco the am 83X 1^14 -'ýZt re A3 ~rM!St Alk
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MTe alopcrp nf the ct.;c, is t±hc 1---.~d~rtion of Fig. 56 IMI1-cate s mailmu deptalence of approximat'ely 1e0,27 for the val±ues oi wrAn Pe represen'Ad. T'i'. res$. t 13 apprv.imate.Jy the mom sm IiheV ;!;
served for the Othcz two CH4 bwAjsd. Mhe curves in the riot.-haa ;ortionof the figure do not exhibit regions having slops of ap3pzoxiitely 0.5,as do the corresponding curves for the other bendls, since the iarg matvaluesi ur a~brbea euuevaLriuu eaplyed were not sa.±ficiently smat forthie lines in this weak bend to exhibit 'introng-line" properties.
Because of the absorption by "12 and the 1Unitad eacunt of data ob-taled for the 1550 cu 1l band, It was not possible to datdaraine the ),enintensity with very high accuracy. the value of fA(%b)4w indicatei by the;aizatet of Fig. 56 of coivrse does not Includea absorption by the 1-branh
of te vban, site nlythe bsoptin atfreuen iegreater than
tersined by e;.ttt ';at~ing the cwvee of Fig. 56 wou.ld be too low. Rowt:,by txteowlatizig th-se ,tr,,v aw-4 b-f a".intirs! that the couri)uation
of Cie P?-crarch ....Mpn !ath'y the suwor as the 3-btaach It. can Ue ecu-sated that. tLL ablCutoI ±MthbP tvu ot the w-. be-ýd is betee 2 "sA 5atuAel C.r To Lha knowv *dge of tas rAtios, the Irlzaully of thiwebA baral ; %. wt~d woni sain rLA y!0-iIrmij.
In order to obtain more accr.~e values for %be I U.&Ittc of taeC4~ Uaols, 4!4her *c~lues o: kjuiv"&zet pre ss~e ba.ao. b*e u&44 =11 &,e4&%& sboua.4 be obtained for iiqies hAv~ng snu valu'e& .f schwbeia nu-gentratIco. Us the case of tUe 1550 call 14.3d. the C4a r. izue'"d be,4zIwA sd a 4j*..reawtt~r vwhch could be evexuatd or therouaa4~ Arise,sbo*ald be US". TAIS GXata Care VGP mOt (Akas u1244 the dAlATMIJSMof beand InteislUse me osily or 3econDAWy l~owtanee in the 1"sc~t
In order wo obtain vjjoL-1u2a1 e;Z'ato&& t, roeat the to?.l &U&tied of the 3= aw ~'04- t tM P"fldUS V MAd P", %MU e~avs ofFig. S5i ware drawn with the variable, We'" Gi JA SheniSe. 'MA Vai'A*0. 4 wa' arived at from Ube 01spee of the ller Portin of tus curve"of F4g6. 52 end 53 1-. :A* a#,* eaamr as vas dw % far tM 2M ca'1 Vgbas -%e pniasi cmrvrWvs~.ia %.. trbe "Vertact #l'wa of piseeure is
V c very Ciost Umquter ovor 4 * "*alks Of walml '.0 W "' severAl Of' Q9e VWVVeS ~re O LWta teN the t~r&,W
uj SV%,rIi A d' L bul, ~se pvaI~a ctsrroopmaiig ur %L.. 4.Lt'atea%cc40A4 Wart UWý.: *-,#.& Ua -. 11U ro1A'vvt, 0e'pwe" wI's. 4*.
rived Mnr the A:V ca- 44 huh
15 fv) <~ '
10 P, fltM A
I 1lpI%,4.W 1 , , -
-II4!
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N\.•
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for fA(v)dv - -375 + 272 log wPe OA
and10 < Pe < 300•o Hg. (4i)
Valuea offA(v)dv determined by use of the above equations areprobably accurute +n +÷e4, except fcr ' jlucc offA(v)dv < 40 ca-", belovwhich the .urror mighL .e- as gre-.at a ±15%.
Figure 58 shove the Lotai absorption of the 1306 cu- CH4 band aortainste and vPe0 . 6 as the abacicsa. The curves are not as close as inportiow of Fig. 57. It is possible that a somewbat different value ofthe exponent ol Pe could be used to cause the curves more nearly tocoincide' towever, the various ,-urves in Fig. 58 dL not 4 orm t'ae ree.e-tiver' -' . . t.Lez- occurring In the corresporAing figures discuseedearller; for example, m porticn -f the curve corresponding to 10 1 Rglies between the c;ruves ,corresponding to 50 M Hg and 200 - Kg. ItIs apparent that an increase in the value of the exponent )f Pe vouldtend to cause the two curves corresponding to 760 and 50I V g to eeocm!loser together; but on tbe other hand, the curves corresiondAL. t,%•v m ag arnd 5'Q Hg would Me rurther separated. The value 0.6 vea
skt a nouljnl value for b.te exp'-nent.
Since the curves of rii. •8 are not Rq c1oee togc~tlr as the corre-sponding curve, for othei b•n~s, it is probable that any espirical equa-tiona derived from then would be lens accurate than the equations derivedfor the other bands. The following equations whieh wre obtained forthe 1306 ca-1 C34 band are believed to be capable of yielding correctvalues of to÷tl abeor ion to vLthin 115% for the eortitiona specified.:
for fA(v)dv - '(.5 [vpO.O6O'.6
and~ c <JA(v)dv < 130 ca~
J)Aý v;.iv 19r 4, '11 lob w.1 U6
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VIII. St~U4AEY
The 4:'rk -overed in the present report has n~ealt with the infraredabsorption of the mninor' atmuspheric gases nitrous oxi~de, carbon monoxide,and methane. SaMl'~s 1onsist~ing of t'sese gases alone and in binary mix-.tures with nitrogen hawe been investigated over wide ranges of absorberconcentration w and total pressure P. From the observed absorption foreach band, it has been po~ssible to present curves ahowing total absorp-tion~fA(v)dv for various values of absorb~er concentration as a functionof equiv.alent pressure Pet vhich is a parameter that Includes the totalpressure P nrwd a small additional term proportional to the partial pres-sure of the Rbotorbing gan; the mnanitiOP of the additional term is Alsodependent on the value of a aself-broadeaing coefficient," defined inthe report and measured experimentally for each abs:oirption band. .' otherset of curves for each band shows the total absorption for various equiva-lent pressures as a function of Akbsorber concentration. The curves pro--vide a basis for the prediction of total absorption for any values of vwAn Pe. included in toe wide range of these parameters covered in theattidy. Extu.nsive tables included at the end of the report provide addi-tional absorption data for use by other investigators who my be interestedIn atmospheric transmission or in more general problems of moeorption.
The experimental renults are@ compared with various theoretical pre-dictions. For values of v ani Pj for which the "strong-line approximation"predicts the dependence 11A(v) dv;%PfvTe, it has baee fouSAI that fA(V )d V iindeed roughly 1:roportional tv -jV7 but not t~o 4P; For sufficiently largevalues of P, overlapping of lines cause~s total be-4 absorption to approach"a "saturation value"; for very low values of P, the total abuirption for"a given absorber concentration also approaches a limiting value for whichthe Dzppler broadening of lines, Inlependent of pressure, predomlnatee.
It taz been poscible to .ýbtain empiricatl equeations relating 1tot2absorption to v and Pe for certaix' limiPed values of total aboorptionJA(v)dv and equ-ivalent pressure Pe. The limits of validity for suchequations are discussed. The empirical squotions are slywarized inTablu (.
By stuW~'Ig total absosrption at smw-11 values of abnorber concentre.-tion v sana auficier.tly large vulues of equivalent pressure Pop It 'asbeen ;osaib'le to ubtain valuez for the band intenfitj ft(v)dv for thvarious bends studied. 'rei~eat reutvaua up: it.h thevalaus reported by other Investigators. Tk.e values obtaiao& for bend
A se-ond We ivf ',rimpay'sons of the present results with sAmistingtheories has involved iatudies of the absorption A(v'I In spectral rpm anT. sximum absorptinn wa the P- -ind R..branches of various banda. Iiim**ý Nnsec it vaý f:.nd ttAt A, 0i- -1v ovr vousia M ran or V Wandhowevur, it ano rcoind tjiat the proportionality A(v )-,P was rarely
113
observed. The possible effect of weak lines adjacent to strong one01 isdiscussed as one cause of tl,e failure of the "strong line approximatt.-"':voak lines are always present in t.he wings of absorption bads, buýsmetimas are not present near the regions of xm•u absorption in theP- and R-bimncbes.
It is hoped that The present results can be used as a basis forthe development of adequate general theories of absorption in the in-fz-ar4 6ýCLT•. 01f darier as well &0 A.,© a ic ,IQI ý 1. i ý1.
studies of the atmosphere.
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Table 1. Jktorlala
dupplior pnrtyi,Gas am Grad. %uit.
ko Jtkdesoaa 99 Chiefly 12, traosaof cog
Co ttheonon C. P. 97 chiefly C02
CNk thi..oa C. P. 99.0 ?moos of Ce16,N2,
'!021 ad 320
N2 Ulid. KIgb Pwl t7 99.99 bIk. of l5 pam"Dr7 at 520 per 1000 cu.
CA - Mimi
lkbl* 2. gof-Ir*&&mu~vg CoerneletaU forMoor Atmoprie OL**s
bmd Sai-Rveade"8 Comtt1.1. VP
M42 co-' it,,0 1.12 2 0.07
A3 em1I cc i. a * 0.06
S:*u t-0 Ir ý nf n
)Wv~4 to- ýk I'"O a 00
'36 cr at a3 0.08
150 CS. 1. 3 a a.0.
naImd~n to Wi. 1) am (Ilk),VMM 92 LO tb* m~tv*ea. 00.
'ft le 1. Data .0ýr t.e Z3.'2= ca"- 320
?L,• IS-. No. ccrrespon•. to, t,, f1rc'z -. vh::.:*& L:. ipectr"um cf ezn m..sieIs cbmm. Absence of Fi. P c,. IMdca?.es specrU= is not £t3D. V-:e.--Alt-:ezýf vslues of A(v) 4nd jfAfvv)dv are d*iscussed in text._ .e Ylg. v We JA(v)dv A1_.4C) A(..13)
Path Ianeth a 1.55 en
o .O.I0 0 1.( 1.W 00 1. .4 BUNT! r = 1:2 5 3.0033 2.0 1. 56 2.1. 2. p3 a &!one In
5 - 0..c•1 3.1 2.03 3.0 '.6 '1,0.5 o.o4 4.6 2.75 4.-,0 -. 6
5 5 0.-011 6.8 3.79 5.5 5..6 5 0.0157 9.7 ,..21 7.5 .".7 5 0.0217 1".4 6.93 9.7 9.5c r 0.Wo2 16.7 6.49. l1.L 11.29 5 n 0352 21.8 10.9 15.3 14.6
10 5 0.0456 28.1 13.b 19.2 18.2I1 8 0.057 35.3 16.1 23.3 21.3
1ý 8 0.091 56.2 24.7 34.c 33.3,4 c.c:7 5.58 15. 21.3 20.615 5, L.0724 ,4.6 19.6 27.5 P5.816 5 0.112 69. 28.2 39.5 -17 5 0. 172 !C6 40.2 55.0 52.118 5 0.225 150 53.2 71.0 68.019 5 0.38 2411 69.3 89.1 85.020 5 0.677 .19 85.2 96.Q 98.3S5 1.3 , 96.8 99.0 100%)
-. 9..0,. *." d*.5 *" - I*7. d•. . ;
2 o.0186 21.6 7.21 1o.; ..6 3o,2, 8 0.016 42A. 9.31 Z. •2.3 Eam=.a 23-30:25 8 c). o-,6 91.: ;2.2 ---. 16..4 i2 added to25 6 0.0186 186 15.8 24.2 21.6 omps 22
0I 6 :1 n _,. "N60 Loa' f 5u.u kci.'d28 8 o.o018 749 22.0 36.o u.829 0.0186 1520 24.4 ko.0 3'. 9
5i a 0.0Ol0 6.2 3.6- 5.1 h.A L.6s re ,r5? 6 0.0101 M.9 4..1 b.0 5.l X•033 8 0.0101. 26.,. 5.60 8 1 7.3S6 u.o, 01 .u 6.66 ., . 535 8 O. 0101 114 9.1X 14. 0 ;2.r,36 8 0.0101 259 11.6 "3.5 16.'. hsmles t' I:
0 -.0101 716 14.4 21.- 20.6 k med to0 0.01C.1 ism0 19K, ?59.Is 22.4 iump, . ~14
n8 o.Z' 3035 15.7 25.6 22.9
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Table •. Data for tLe 2214 cm" N20 BaAd
The T'ig. No. corresponds tc tile figure in vhic,' the spectrum of zacb /is shovn. Absegne ot' Fig. m. indicates spectrum is not haovn. Uncertaintiesof values of A(v) andJfA(v)dv are discussed in text.
Sw•le Pig. v Pe JA(v)4v A(224i) A(2213)NO. Mo. (-+,moo CM) (M us) (czIn) $
Path Lencth a 1.55 ca
1 5 0.0036 1,0 1.00 1.5 1.. kuplrs 1.21 -5 0.0033 2.0 1.56 2.4 2.0 %0 alone in
3 5 0.0051 3.1 2.03 .3.0 2.6 roll4 5 o.0V14 4.6 2.75 4.0 3.65 5 O.O0iO 6.8 3.79 5.5 5.16 5 0.0157 9.7 1.21 7.5 6.87 5 o.%0217 15.4 6.95 9.7 9.5C 5 0o.070 16.7 8.49 i1.8 !1.29 5 0.0352 21.8 10.9 15.53 14.6
10 5 0.0456 28.1 15.8 19.2 18.211 8 0.057 35.3 16.1 2ý.3 21.312 8 0.073 44.9 20.2 28.1 26.61! 8 0.093. C6.- A-.7 34.0 33.014 0.0"4,1 '3.8 I. 21.3 20.6
15 5 G-.07214 4.4.6 19.6 27*i5 P5.816 5 0.112 69.4 28.2 39.5 .7i17 5 0.172 106 40.2 55.0 -2.118 5 0.225 15C 53.- 71.0 68.019 5 0.389 2414 $9.35 W5o20 5 o. 67•719 85. 2 , 98.31 5 1 % 96.8 ".0 100 U
w 8 0.0185 11.5 5.93 8.. 7.7 10. 5 Vg of25 8 0.0186 21.6 78 41 10.i ). 6 ,024 8 o.01t6 b.ik 9.o % P.) a.o P1 1-30:2 8 o.0186 91.2 1: .9 16. 0; Mq sd.a to26 8 0.0 0o 6 15.0 .60 2 21.6 mw1.. ";e( 8 n 0A; Aw I8 ;;.u i1.28 8 0.018C 714 22.0 36.0 51.629 0.0186 1520 2h4.", 40.0 9.!A 6 01.o6o 03, ,.9 ... :
31 8 0.0101 6.2 3.2. 0..1 4.4 5.6 aorYd 8 0. 0101 10.4 it.2le. b.0 .1 1413, a 01o01 26.,o 5.60 /.3JA 8 U.0lv 4). U 6.86 AC. 'v.M5 8 0.0101 L14 9.1, Ilk. 12. 136 a 0.0101 039 U..6 1 .1.6 A6.5 Rampef V~337 A 0.0101 746 ~ 1h4.1 23. 20.6 92 "44t.18 a 0.o11Icaxi~ 15.4 ?5%.4 22, e MP 'a I.%)539 a 0 -- r'1V 3035 15.7 15.6 M2.9
'I/
Table 3. (Continued)
awlel Fig. P, ... ,•.v)dv A(%40•) V2213'...]•)
11o. No. (&too$ cm)~ ') (cm)
40 7 0.0101 56.6 74.3 11,1 10.2 WIo *41 7 0.0101 IV 9.4 l.7 1).G 56 = of mix-42 7 0.ol 264 11.9 19.0 i6.9 ture of 1/10"13 7 0.0101 759 14.4 24.1 20.8 12 an 9/1044 7 0.01.01 3055 15.5 25.8 23.3 N2. Ga. 41.
44.W- id~edto aalp1e 40.
45 0.005k. 3.4 2.32 3.3 3.2 Smle 45: 3.0S0.005o 6.6 2.59 3.6 3.5 -= 8 of N20
47 0.0054 12.1 3.14 4.6 4.2 &lone. S•Ie3Ik 0,o5 nS .,A). 4 AL,2,. 6.3, 5.9 46-h8: k add,-',
to u"Alo 4).
)b9 7 0.0054b 30.1' ".18 6.2 5.7 hm* Ii9: 3050 7 mock 72.0 4.4&Q 8.;. m. e Mg of 4/1051 7 0.0054 19 7.0 U ,2 . o. . 'r,.52 7 0.0051' V 8.. -IL, 5 b"Ilg !..j-54i53 7 0.0054 750 d.6 14.*' .,2.
5 " 7 ).I0'ri 3035 9.05 15.1 .6 !2..6 49.
56 0.0032 4.2 IM7 2.6 2.3 1.75 Be ofl5T (0.OC52 9.9 2.09 5.2 2.9 * ,a58 0.0c, 4-.T f.61 a 4.o .; "
590.0(5 2 35.01 5.21 5.2 1'.6 ad , Id o som-ple 55.
0 I u.uu)2 11.1I 253 3.8 3.5 sople 60:61 7 0.0052 4O.1 . .21 5.1 4.5 17.3 i J4 of62 7 0.oo22 105 1'.20 6.8 6.2 1/10 N~O p1.-65 i C!- " it.96 8.5 7.5 twoe. hoM108A 0 .uv ?% 5.40 4,:: 7.' ý;6-45, I
65 7 0.0cci 3035 5.57 9.? 8.3 oA"4 to iwe.ple 60.
66 15 2.5 2.2 "1 62B 7 n.oO •o.¢ I.kq 1.,8 IS I./ho W4 six,
TO 1 .',"gO !T= *k,• 5.5 'ti8 • 67-721 %71O.0m IT.,,b 6.1 5.R 0"6 sa
72 7 0.00v ._13 5..: P1.0 a.
JV
Table 3. (Continued)
Q9emle Fig. v * A)d'A(2240G) 1(2213)~No. No. I~tms eft) %~~3:. a
73 7 o.OO0. 6.1 0.98 1.5 1.3 Sample 75: 6.074 7 U.OoUI 15.6 1.22 1.9 1.6 g % of 1/1o75 o.On IL 39.9 3 .54 2.4 2.1 o20 mixture.76 7 0.0011 110 1.75 3.0 2.5 Samples 74-79:77 0.0011 259 2..90 M. 2.8 N2 added to78 7 0.0011 745 t.03 5.5 3.0 sample 73.79 0.001i 3035 2.03 3.14 2.8
8o 6 0.0o0l 30.1 1.3 2.3 1.9 sample 8o:81 0.0011 746 1.95 3.4 2.9 30.0 = g or82 6 0.0011 3035 2.00 3.5 3.0 1/50 o20 six-
tore . Sewles81..82: 2added to sam-ple 80
8, 6 0.0oo7P 20.1 1.03 1.6 1.4 Sespl,. 8!- 20.134 6 o.00072 98.0 1.21 2.1 1.7 i 69 of 1/5085 0.o0o7, 250 1.30 2.2r 1.9 %o mixture.66 6 O.00072 746 1.30 2.3 1.9 Samples 814-87:87 0.00072 3035 1.33 2.3 1.9 vin adeto
sample 83.
66 6 0.00047 13.1 0.70 1.1 0.9 wlle 88: 13.189 6 0.00047 3035 0.86 1.5 1.3 f- 4 of 1/50
520 r Lture.h l, 89: "aadded to saple
90 6 0.00033 9.2 0.55 o.8 0.7 iam. e 90: 9.291 • -O.0033 3035 0.62 0.9 U.8 -M :, a ij5o
520 mixture.Sample 91: 16eadd" to sam.-'pIe 90.
S 6 0. m0aý 6.5 0.37 0. .5 Smple. 92: 6. 55 .o0 -3!5 0.3c, 0.~ C- = 19o /50
Z;mple 93.- 92Wedd to ama-
ple 92.
119
sampla rpig. 2 "0) A.(2213) ARpmO) A, 1;NO. 50. 1et~ Em % 16r~
94 6 0.00016 4.5 0.27 0.5 O.A Somle 9): 4.5,5 6 0.00016 3035 0.35 o.6 0.5 ,m B of 1/50
320 sxt=o.Semple 95: N2added to a-ple 9)4.
96 7 0.00017 h8.o 2.18 3.4 3.2 Sales 96-9? 7 0.)033 93.0 3.93 6.)4 5.7 101: 1/50 32098 7 o.oo6o 165 6.96 11.2 9.9 uvzxture alone.99 7 0.0098 270 11.33 18.3 16.1
100 T 0.0136 375 15.)4 25.0 22.0101 o.W3 618 23.7 37.5 33.5
102 5 0.0016 9.1 1.50 2.1 1.8 Sau.leu 102-1.3 0.0024 1it3.3 1.V7 2.7 2.5 112: 1/10 320104 5 0.00o2 17.8 2..•3 3.8 1.1t ,tur- aone.105 5 0.0045 25.8 3.5.4 5.1 .io6 5 0.0065 36.4 4.82 7.3 6.6107 5 0.0091 50.6 6.h6 0o.o 9.0108 5 ,.0o185 103 12.176 19.1 17.5109 5 0.4295 165 19.50 28.9 96,311o 5 0.0500 281 50-7C . 5.4 )43.e1i1 5 u.050 )418 41.90 61.6 56.6112 5 O...u5O 644 57.00 78.8 75.0
P&Q2 LspAMt 6.35 cm
113 10 0.0371 5.6 .1.4 8.5 8.35 Samle 1. 5.011.4 10 0.03o1 8.1 7.0 9.3 8.97 m 6 of 56o.U•11 o 00.0371 11.8 7.9 1o.6 10.1 %•k,,.. -4.116 10 0o. 0o31 20.5 9.6 13A ' 12.5, &"0, 3 ,117 10 0,0371 T 32.6 l.,* 1.2 15.5 to sawle 113.118 10 O-o.0,T )49. 13.7 19.6 .8.0119 10 0.0371 98.1 17.6 26.2 23.8120 10 0.0371 182 ki.2 3ý.2 31.1121. 0.071 29 26.2 41.3 55.01;• o~• --€ 6.3 8.3 8.2•.
12. 30~12)4 0 . j. ?1 13.9 19. 17.9124 10 0.0 11 4 "27.9 43.) '7.6125 10 O.0O37 755 32.3 1.0 45.0L'6 0.0371 o 5iYo 3.9 98.0 52..417 0.- " -2300 37.9 9.5 5 "4.61.08 10 0.0y71 50T0 37.9 59.5 5)4.V
Tab 5iI .. (Cuuti iei)
iqo. no. (atus CM) (--1 )J {c,-) _
129 10 0.074 11.2 11.5 15.7 .5.3 okqle 129;130 10 0.074 21.2 1..5 20.0 18.3 10.0 m as of131 10 0.074 51.2 19.8 28.7 25.7 120. Sawlem132 10 0.0714 103. 26.0 39.0 314.2 130-135: 12133 10 0.071 200 33.2 49.7 3.5 adAed to am-134 iC 0.074 100 .2.7 65.5 55.5 p1, 129.!.M 10 0.07,4 7140 L49. 75.2 66,5
136 0.oV71 11.2 11.7 15.9 15.5 G3.E 1lb:1311 0.074 101 25.8 38.7 34.0 10.0 = 1, of138 0.074 741 8.6 714.5 65.7 Ig0. Gaqiles139 0.074 1485 54.0 83.8 76.0 i,-111: 3211.0 o.o1 2295 55.5 86.0 80.5 adde to ams-141 10 0.074 V 075 56.3 85.7 81.2 pis 136
142 10 0.148 22.4 22.1 29.6 28.1 kM1. 112.11,3 10 0.18 3.? 24..5 34.0 12.0 20.0,m = of144 10 0.11.8 52. 25.8 39.7 3T.2 V4.qa145 10 0.148 105 37.2 53.3 48.0 1.3-51:t %.
116 10 ,-.l1. 199 45.5 65.9 59.3 .4.4d to m&-1.7 iu ý..1•8 395 56.2 79.1 72.0 p1. 112.118 10 o.I1. 718 62.o 90.3 8$3.011.9 0.11.8 1655 68.5 96.3. 91.5ih 0. IW1 2315 70.5 95.5 9..o151 10 ).148 120 71.0 96.5 95.0
i.i 9 0.37 ,6 h6.9 60.1 59.3 1,e 152:• -40.9 .7 1in 7.6 Th.7 72.2 m I# ,t P.
0 0. I7 225 67.2 b5. 62.7 b3..eso153-.!1*-) 9 0..37 388 T5.2 ^0 %.8 91.Q 1601 32 ad"154 0 , 'I. 559 8e.1 97.2 96.7 to o,.e 1521.157T .. . r 709 00.a 97.1. 97. 1158 o.Y, .21.1 82.8 97.9 98.1
1&;I4 9 C.3 Tr OT 814.5 9G.2 98.9
161 9 0.71. A:2 70. 1 66.5 85.0 Ihe 161?16Z 9 0.71 131 TT.F )1.3 91.9 100 - Is of3 r., 0.71. _Iqc )6.6 76.6 Vo. suits( 0.71. h79 "U:.o 958.6 46.. '%b-1671 N2
165 9 c.74 767 ). n o9.O .O 9.4 ,e44d to mas.)(60 -74 1550 A2.2 99.5 99.6 3. 3.61.
167 9 0.74 Y.& 7.5 ý?.s 99.8
Table 3. (Conittnue")
rAmple Fig. v P, jA(vldv A(22'40) A(2213)
168 9 1 1 227 91.4 98.7 99.1 Suie 168:169 1.51 365 9'1.1 99.5 99. 6 201 m F& of170 9 1.51 769 97.8 99.9 99.9 N%0. BSAqle171 1.51 1545 98.8 100 100 169-173: W2172 1.51 2360 98.9 100 100 added to ma-173 1.51 3105 1o0C 100 10 ple 16 8
174 9 3.02 456 10j2.1 LOO 100 bwlie 174:L'5 3.02 611 103.3 100 100 4o0 m 89 of
177 3.02 1570 10o5.6 100 100 175-178: we178 9 3.02 2365 105.0 n .00 100 add4e to "a-
ple 174.
179 6 0.00?7 4 1 2.0 2.6 2.6 %Wl,, es .79-Lao 6 0.01.11 it. ý 2.8 3.0 16J6: %,O alame .181 6 0.0148 2.2 2.8 3.9 '.8
180 ~ ~3.5 4.52S" 6 o0.=23 5.• 3.• 5.1 •.7184 6 O.0f7,6 4.2 i.9 (..6 6.5let, h O.OT) 1.1.2 Ill.," 16.o 1ý.8
186 6 0.113 17.0 17.5 22.6 22 1
'57 11• 1.16 3.a 3. 6 .4 36.4, Pawl 1 1 2.9
150 11 5~ . 8.7 45.2 46.68 I of %0~.L89 11 1.A Ie.8 6.b 54.9 56.o a•ml.e I-190 U %.4 30.0 7o.5 ",.4-5 19k tp aded4191 11 L.4k 7'.0 80.0 91.! 91. t') aple .19e 1 IAh 1!.p OP.ii A8. 4 aeilA37195 1.L 1.6 795 B.8 90.! 1O010h 11 1.4, 5055 101-2 100l- 100
196 11 2.8 15.1 64.1 ?7.- 75.0 ;.8 -m 4 of!,o 41 2.8 29.p to'; '.. of., ;j%. Ua1mvIIna• .1 2.6 71t," 92.-;, 1.%• .• 20.- .199 .I 2•.C 22 161-, 09.• 100 add"4 to •m-
21.%) 2.8 7h5 106.s 100 100 pit '11!201 2.0 50m 106.2 100 100
U--2
Table 3. (Continued)
MII 71RE v P.. rA(v)d~v A(22410) (23-No. So. (&tuos CM)('g, CM1) ~ % R rks
202 1U 5.6 13.9 79.9 87 • 90.0 Bunle 202:203 11 5.d 26.7 916 96.i. 97.0 12.4•= Hg of204 11 5.8 64.5 100.0 99.0 99.6 N2 0. Saples205 11 C.8 197 10a.5 9).6 1oo 203-206: N2206 3 11 5.8 750 1'3.4 100 100 added to am-
ple 202.
207 11 11.6 28.0 102.0 99.0 99.5 Semple 207:208 11 11.6 61 108.8 100 100 25 = Hg of209 ii 11.6 203 115.7 100 100 2o. SUaml&It,
added to mQ-ple 207.
210 10 23.7 56 115. 100 10c Semle 210:211 10 23.7 10, 120.1 luO 100 50.3 mn• Hof212 10 23.7 211 125.3 1o00 100 o20. Smple
211-2,12: H2alded to tm-ple P0
21. 10 1.39 5.4 32.7 37.7 40.0 Samp-le 213-:t1j 10 2. • 5. b 45.8 52.7 54, 5 216: %0235 10 3.70 9.0 62.5 72.2 73.4 alone.216 10 5.56 13.4 78.3 85.4 86."
ft-. Lers.t._. 80-1;
",. 18.8 22.4 103.2 100 O0 Semple W11Ilie 18.8 h2,e 108.7 100 100 20.0 msN of219 16.8 10 .15.2 • •oo 100 KO. iaamplas22 18.6 W11 1PM.• IT 1r. 22I-2ci: k221 8.3 7h2 121.8 1,A 100 -de to eam-
pie 217.
.. is.. ".6 L25 100 Irc0 Sample =22tr- 6.4. 168 1Y 100 n h.0=usi
~ ~ I. 211 w ~ ;.1 L0 W20. Sample$
e644,e to os.
1234
TaLie 4,. Data for the 2145 a- CO Banc
The Fig. No. .eorresponds "-, t). figu!re in whiie• the spectrum of !ach c'a cis shovn. Absence of Fig. No. indicates spectrum is not shown. Uncertaintiesof values u" A(v) and JA~v)dv are discussed in the text.Sample Fig. w Pe rA(v)dv A(2166) A(2119)
No. No. (stmos cm) (mm Ha) (•-1) I tearks
Path Length = 1,55 cm
1 23 0.00096 5.4 0.14 o.18 0.20 Sample 1: 5.42 0.00096 107 0.24 0.25 0.25 M Hg of mix-
o0.0o096 670 0.26 0.30 0.30 ture of 1/1o4 23 0.00096 3020 0.27 .32 o.032 CO ma 9/10 N2.
Samples 2-4:N2 added tosample 1.
5 23 O.00154 49.5 0.31 0.36 0.37 Samples 5-7:6 o.oo154 313 0.o o.43 o.4o 8.8 mm He of7 23 0.0015k 3040 0.39 0.43 0,40 mixturo of 1/10
CO and 9/10 N2added.
8 23 0,00262 15 o.36 0.35 0.31 Samle 8: 159 0.x0262 40.7 o.45 0.A7 C.1" -=U of Mix-
10 23 0.o)62 1o6 0.56 0.65 0.56 ture of 1/..o11 o.o262 256 o.64 0.12 0.65 COa M29/1uN2.12 o.=0262 738 0.68 0.74 o.63 GampleJ 9-13:13 0.00262 3020 0.69 0.76 0.70 N2 added to
sample 0.
14 23 0-00455 2Q, 0.53ý o.50- 0.50 Gww1e 14: 25 mn15 o.o0435 68 0.68 0.70 0.68 H& of nixture16 23 0 00435 "45 0.91 1.0 0.85 of 1/10 CO and17 0.00435 619 U.99 1.1 0.95 9/10 52. ba-18 0.00435 1315 1.0. 1.2 1.0 plea 15-19: N219 0.00435 V20 1.09 1,3 1.! ad to *Vle
14.
PO 23 0.00703 40 o.84 0.85 0.7 Sample 20: 4021 0.00703 93 1.10 1.1 1.0 = H6 of wix-M 23 0.00703 220 1.40 1.5 1.2 ture oy 1/10 CO2t 0.00703 410 1.60 1.7 1.4 and 9/110 N.44 u.uu/uI 1520 1.87 2.2 1.7 SMMPle, 11--25:25 23 0.00703 300 1.91 2.2 1.7 N adied to
esaple wo.
124
-L O • E I i |= ,•' =_ r. . .
Table 4. (Continued)
9mzple Fig. V re WIAV)4 "1"• -(P1]Wso. no. (atmos cm) (m 2g) (c,-) %
26 23 0.0107 6.1 0.48 0.40 0.38 Semple 26: 6.v27 23 0-0107 25.0 0.84 0.85 0.70 ,-Ha of Co28 0.0107 52.0 1.11 1.10 0.88 alone. Samples29 23 0.0107 118 1.51 1.70 1.40 27-32: 2 added30 23 0.0107 314 2.14 2.45 1.90 to sample 26.31 23 o. 01.7 720 2.50 2.95 2.3532 23 0.0107 3020 2.83 3.140 2.70
33 23 0.0176 1O.6 0.81 0.73 0.72 Sample 33: 10.034 23 0.0176 22.2 1.12 1.1 1.0 = Hg of CO35 23 0.0176 49.9 1.63 1.5 1.3 alone. Samples36 --3 0.0176 157 2.55 2.6 2.2 34-39: N2 added37 23 0.0176 412 3.1 3.7 3.2 to sample 33.38 23 0.0176 1005 ,4.14 14.7 3.739 23 0.0176 3020 C.6? 5.6 ".
40 23 0.03Q62 20.9 1.57 1.k 1.2 Samle 40: 20.541 23 0.036U 45.6 2.32 2.2 1.9 mm Hg of CO42 23 0.0362 131 3.79 3.5 3.1 alone. SaMles43 23 0.362 254 5.10 4.9 4.2 41-46: n, added44 23 0o.362 692 7.09 7.14 6.1 to sample k).45 23 0.0362 1520 8.143 9.3 7.446 23 0.036P 3020 9.33 10.3 8.1
47 23 0.0722 41.8 3.39 3.2 2.7 Sale 47: 41.0)48 23 0.0722 8ý 4.70 4.3 3.7 = Xg of 0049 23 0.0722 1k). 6.75 6.2 5.) alone. Samples50 23 0.u(i22 3T 9.05 .7 7.3 46-53: N2 added51 23 0.0722 788 11.97 11.9 9.9 to samle 47.52 23 o.7-22 1520 I14.65 1).14 1.2.553 23 0.0722 3020 16.76 18.14 114.6
54 29 o.165 95.90 0.3 7.3 6.14 ••mples 514-59:55 29 0.349 203 17.6 15.2 13.8 CO •lune.56 29 0.709 41; 34.14 29.3 26.157 29 1.31 761 60.7 51.7 46.158 29 2.67 1555 10c. 814.5 78.759 29 5.52 !210 157 100 QQ.7
Table 4. (contin±ue'd)
Sia*Ile Fig. Fe JA(V)dlv A(2165) A(2117)No. No. (atmosc (m k) (CM-1 ) % Rwk
Path Length - 6.35 cm
60 24 0.073 10.2 1.8 1.4 1.4 Sampip 60: 1061 0.073 16.o 2.) 1.8 1.7 = H9 of 0062 241 0.07) 27.0 2.9 2.2 2.1 alone. Samplaz63 0.073 45.0 3.7 3.1 2.7 61-70: 14 added64 24 0.073 86.0 4.8 4.1 3.5 W sample- 60.
170 6.2 5.7.6 24 C.073 292 8.0 7.5 6.3
67 0.073 492 10/'l 9.5 8.168 24 0.073 735 11.7 11.5 9.269 ch T 03 1515 -,1.5; 1-.0C 1-3.270 24 0,073 2970 16. 3 18.1 14.1.
71 24, 0.145 20.4 3.6 E Il. 1 P-.$Rnl~e 71: 2.072 o.145 32.4 4.8 4,n 3.7 =H6 of CO75 24 0.145 4q.8 5.6; 4.7 4.2 slono. Sa~1esT4 24 0.145 88.5 7.2' 6.1 5.4 72-80: %2 added75 24 0.145 152 9.1 6.0 6.7 to BAmmle 71.76 0.145 21;2 12.0 10.8 9.177 24 0.145 545 15.9 14.6 12.378 0.145 797 18.7 17.5 14.979 0.145 1545 23.6 23.2 19.380 25 0.145 30740 28.7 29.5 24..0
81. 24 0.298 42.0 7.6 6.3 5.8 sample 8:.: It182 24 0.298 64.0 9.2 7.7 7.0 Ma 96 of CO83 24 0. 98 95.0 n1.0 9.4 8.3 almnn. Sawisa84 24 0,298 1'48 13.4 11.4 io.4 82-91: 112 &ad~ tO85 ~h 0.98 21 16.3 . 1 2.3 :m~ i86 24 0.298 333 19.5 17.0 14.987 24 0.290 450 22.2 *~.0 17.188 25 0.298 747 27.5 24.1! 20.589 25 0.298 1470 35.8 X2.8 27.790 25i 0.298 2260 42.0 40.0 33.091 25 U.296 2960 46.3 44,2 36.2^
92 24 0.440 59.0 10.9 8.6 8.2 Sample 92: 5893 24 o.44o 84.5 12.5 10.7 9.6 am F% of WO94 24 0.440 153 16.5 14.0 12.7 alouG. Samples
96 26 e0.44o 341 24.5 20. ti 1d.3 added to aempl97 26 0.440 466 28,Q 24.0 20.8 92.98 26 0.440 727 34.0 29.0 24.799 0.440 1240 42.4 37i 314f
100 26 o.44o 1660 148.7 42.6 !4,2101 0.440 2160 52. 47.6 4o.3i02 2ý o.k40 M95 58.8 53.3 45.
12u
Sample Fig. w Plý fA(ii)dv A(2168) A(2l16) - '1b. No. (ataos CM) (MM Sig) (cia 4 ) Reai
103 26 0.800 112 19.9 16.2 14.3 '*,Vle 103: 110104 26 O.A00 169 24.0 19.8 18.0 mm iHg o CO105 26 0.800 247 27.9 213, 20.8 alone. R.ea-_0.o6 26 o.o 8w 35.1. ?9.5 26.2 104-1Uk:
107 26 Q.8&0 51) 39.5 .. 29.3 added to sample1.08 26 o.8oo 748 47.1 O., 4 4.8 103.109 2-5 0. so0, !Z6 -5... ' 9.•6 43.l11a ý?,6 o. 80L.- 1615 (4 .6 c556 48.2
11i *26 u. Fv( 22Z5 7.? t:,2 0 54,4112 26 0. 800 2940 81.3 0.5 6o.5
113 26 1.48 207 37.5 )0.0 27.5 Sample li.3; 203114 26 1.48 304 4. 56.o %.w Mg of CO115 P6 1.48 461 54.5 ~43.2 39.0 alone. 1F1ames116 26 1.48 752 56.5 52.8 47.P 12),-120: lI,117 1.40 l240 81.5 64.o 57.0 added to sample118 26 1.4A 1960 95.-) 7•4.3 66.2 113.119 1.48 2310 100 78.5 7o.';120 26 1.48 3060 110 82.,) 76.6
121 25 2.?4 4'12 70.2 56.0 ql.O slape 121: VA122 25 2.9Q4 591 80.2 6..5 58.5 m E, of CO123 P! 2.94 85! 93.1 76.0 66.0 alone. Smlea124 25 2.94 1.275 106 80.d 74i.5 122-17T:%125 25 2.94 177o 19 8&.8 81.5 added to smple126 2.94 2295 127 52q.8 88.8 121.- 2, 25 2.94 "-2qs 9i,.,96 91.2
128 25 5.55 7M I-,) 84.1 79.2 Sm1e 1281 ?62129 25 5.55 1180 129 92.8 84.2 -i, C of CO130 5.55 1465 138 96.o 91.3 4 ,,ne. 8MbV1*131 25 5.55 1815 145 95.2 95.0 129-133z 52132 5.55 2295 1152 98. 97.0 aded to sample133 25 3.55 29)5 158 99.2 98.4 128.
131& 25 10.9 15130 ! 99.7 96.8 S1a1 134;1!5 1u.9 i.•o 169 100 99.3 1500 o ft of136 10.9 2295 172 99 7 99.5 CO alan. a•-I.- 25 10.9 W85 170 100 9Q. I plea d135vs-TI
ad edled to=ample i ' ,
Table •. (Continued)
SaWle Pig, P e JA(v)dv A(27M)~ ___U6No. No. (,tOD, CM) (M RX (M,-1) % $, •"••"
138 25 16.6 2325 182 99. i ,. 6 smqvr 138:139 25 16.6 3140 187 90.7 )9.7 2280 mOeg of
C-) alone. a-.pIe 1.39: 2added tI. am-Ple 15ý.
22~.2 3115 194 99.6 99.6 SLIP1 140:300 lone.
Pat~h langth . 4w cm00 al ne
414 1 1.2 3.0 6.0 .4 45 spiels 141.- 2.9
142 27 1.-1 5.3 6.9 5.2 4.9 = It ,,r FO1h3 27 1.32 10.0 9.4 5.8 6.6 al.one. Smages1 27 1.,2 26.2 14.2 10.9 10.0 1I4--19: Ng1l 5 27 1.32 61.a 19.7 15.6 14.T "Me• to mm1e1V6 07 1.32 170 33.6 26.1 24.2 11.14T' e7 1.32 503 51.8 4s2.2 58.3146 27 1.32 1520 81.9 66.81 6001.9 27 1.32 E70 1). .6 81.8 74.0
V.O 1 3 .62 5.8 1c.0 6.8 6.6 Ema 1: 5.?151 e8 2.62 10.' 1r.6 9.o 8.3 - o• 00I1S W D 1,2 29.9 20.5 1.5.0 1b.9 alow. 6mlee15? 20 2.6 *6O ga 1.4 111T
I's M .G 4i.7 36.2. 35.5 add"~ t3 "Sol#155 28 P.621 503 73.2 56.7 52.2 ISO.156 16 2.62 1520 1149 81. 7).b157 28 1.6e aVgu 1..•5 ".0 go.n)!A go 4.AR 10. 17.8 13.6 12.9 .l, 158t 10.71q 26 4.62 g,.i 26.0 2, o of .o160 W 9 65." VA.8 30o.6 . so. sws
16 ~1714 60.P 47-5 M1.. 199-164,to 28 4..Q 530 '.6 71.7 66.M? 4Od to paele163 26 .. @@ 15,20 1ý., ,. 9. on. IV.Ibb 20 4.02 "TO 151.02 .,. 77.5'
AM
Table -. (ConUmwd)
W e ,,,- pt .! •,P A ) A.2116)
No. N0. (sama. enj (me 38) m ) %165 28 1.1. 2.6. 50.7 39 36.1 , 65: 2167 28 11.1 2 IIn c. Al, o
168 26 14., 756 150.9 ,A 9.6.6 1c6-bu:169 28 14.h 1520 170.1 1o 99.9 addeto om-170 28 14. 2970 183. o 10o 0 ple 165.
"LT1 28 45.6 101 123.3 89.0 82,) M 171. 100172 2 h5-.6 25T 156.8 98.8 97.-1k f of oC173 2 4,5.6 771 1. 6 Loo 100 &Ion*. suqic 4
172-.'3#): 92adedge to siqg
1716 27 0.46 1.0 2.47 1.8 1.8 ao~gat 174.I79z175 2, 0.91 2.0 1' i.5 2- .9 CD aim-:176 27 1. 3T 3.1 5.76 4.. 4..1T7 2n 2.268. 8.70 6.? 6.1178 w1 9.10 20.4 31-90 25.6 33.3179 VT U.8 51.0 73.90D 57.6 5%3.'
Yb1. 5. Dsta f.~r t';* "60 co-! Co ]M
TeFig. No. correapoods t.) tbe t1gure In~ vh~ch the spectrum n ow e&'Maaple is shown. Ab.aeo ui Fig. No. im6.c~tte spectrueina no t thtcvwa.tbat;*rtaintles ouf the values otjýA(v~dw art discussed in *he text.
Samplo Fi R. v pe Parh jA(v)divso. ~. (&tmo. ca) (m ' .u bq.1 3..
1 40 36.6 Sh 625 8.2 49.9 m14of39 T2.0 54 1252 10.5 e"tR e*lI alone.
lk 59 285 54a 6875 22.1
5 ho 56.6 217 625 16.2 12 added t.j above6 "T.C 21? 1232 22.2 sample to total1 4 145 217 2"45 WI. piwosuw. of 2L)
8 28. 21T 485 43.0 mt
9 40 %6.6 40'. W1. ?1.0 addomdto abfoeIC 39 1". .0 04 12)2 A6.? ONVIStototal.
V% 1'24! ON4 -kA5 N~.T poeeur or tim1.2 59 265 koh 4875 WT. m 1.
054u5.6 74448 a,660 to auoe
15 TIA N 4A5 52.6 pr W atfW:' 9 fL W57 T1.1 m 44.
17 "S5 7%4 ;ZT 71.0 ka. IT to "rumof sm. JA.
0~ .. '! 4.0 100 m 14 or CO
143 204 LIt 12W " % NVI to .41*.
W3 hi205 2%45 %Q.6 wteg. t
26 T2 % up q Ao 1.1Z ""to W "27~14-3 UP4 %2 SQe:~ s.9*
P? i iAk ace 4'e
T2. 70 f8 S2 )6:! "too1to.au,"11A ;z3: 51 q m" to at
?be 2mi !0.1 ryq**wV ofT7'11 O ~ 4. ~ 4A 485 9t.~ -m 84
SaWple Fig. v Fe PtQ A(V)d.
1O. No. (amo.. cm) (- 1g) (cm) (..-l) Rmarks
,' 3 16 216 625- 30.3 2C0ý c gof COx• ~ ~~~ o••g •~ . h - -ell
36 572 216 2"5 5-.537 39 11o0 216 M75 81.0
V• '9 146 420 625 - 52 aed to abow39 288 120 1232 58.0 sample to total40 572 1,20 24J5 7,7.8 pzoouu', of! h.oh41 39 L14 .u• 45 105 - ,g.
1.2 .39 116 756 625 53.5 1• aAe t,288 756 1232 70.6 above sample to5 .2 756 2inl5 9i.6 tota iPressu-re
:9756 . • :5 125 of• 74 -Is.
SI N
ir. c'U M M fu
,I a, -,•
1 0! "~~cc
i:~~ c- z~
p0%
0ý 1 :0 ý1ý 1 RO R liC 0 1 ý
j~~. .4 . * * *
0% f- 04 CD MD %a . 0* a D4 ý.
'a ; .,.it
~0 C:: r 400 *0 .do Q ~ C. o dN i- I
0 .
~1
.4 (M 0% t-
b4 b
-4 c
~ 3 r%
or.%
aL.
iti~O¶
W% W% 0 %
or".. .. ..
*1,
i~0' WIN -0 I WI
II-cJ , . 4g%
SG6 •,,: J~ 0 -. . 4•;- .o4 ;
:I t : I t t: t r !P T to'0!
I!do
-- ;I
14 10 f 0 ~ V,? 00
-4 ~ u*I.- WWI
4 44
U-'
-4 ,4c -
e- Lf\l u
-.4
,44al
-*
0;c 4p o % c1tr
cli 0
cq Ji uN 0! 40
4.-m Qý 4 t- -4 . 0' .4i * 000%4 N4 ,-4. 0 N t - t OJ
0u1 4 mc
0 8 - L' c '
t- K
"", Hl 9 914-4 - St M-4C' R I C1 4 '
-4
I~O 00 0 0 00 0 0 .4 14
:,II . , U'. 1 L cE* 0. ON 00
-J W\'0 '
toIt
dT
0'10 I ~ . '. * '. ~ ~ '-N
14 (V
"F~~~~~ 4 Htt-ooc I
-4~~- 00 -O(4J 0 i
~1\
9 N.
'tj
10
l e :' v .D
a C 13, -1'4J ~
10
T. A( .,I - .l
11. jA( V)dV- C + D 1ýgl 0
Ak v Jv can be clalcuiAted by use of tabulated emplril-&l Constantc;In I and 11 a~bove for values of Pe and JA(v)di' within specirje8limi.ts
Band pe JA ( v)dvLand limits c b a C D limitis limits
0.7 15 10 - 0 45 120
21-43 1975 - 2275 2.75 0.55 0-8 20- ,50 4-40
2.75 0.55 0.8 '- 14o -C 4!'.20 0.43 1 20 - 760 ~40 - 1-20
I CA( 61I ?0 -3000 120 -2003clZ, 0-54W I q.~ " .5s 0.4 10 - 760 15 - P50
_CH4_~0. O-3 75 .,72 IQ0.3000 506- 500-150;ý 7.3 0.4% 0.6 10 -760 20 .130
V.6 -'g0 115 10 - 760 130 - 330
go4 2oaplrii'4ý *%ustlas de4iveti.
to.lr .- %4 s om~ary bptvv~n 1ý, te-1 and 1q50 esm1
CLR ",i~ utber band limits riprepent rreaeizietbay.oNt vhtth ther', is ne2.glhigbe absorpIna~ for s#ampleakused in th~e 5fj~r*W :oP'y.
'Dbl* if 3En b u ae 7ZntAmiaamt.
had Aaaint atM~A- co~
ca-~ - 1 2
2.5 * 0. 5
BIBULM~PAPU
1. 1. X. Cbapwu% em J. N. Eovaru, Ctntract V41-099-*ng- Oh io bta,.ýUniv. Res ft e t 1 89) 20, 21 (19k9); Plao Cootract DA.i4ý-099-*us-12, PAport I M- O, WA J. Opt. Coe. im. 42, 423 836 (1952).
2. J. V. doen D. E. barch, &AM D. V111iama, Oeo"yIcal UeserahTaper Me. 40, WND, Air Force ..a*Wrg Fasearch Ceaesi (155i see
*. ImLmre4 Absorption 7*ve for Now Maor Atffeberic ^.atitu*&ta,
R. - iAdOnb~r$ WA F II.I.bs, Ana&. Riysik 42, 181 (191.3).
5. V. M 1Zlaazar. kSrvard lbta'ralogleal Studies No. 6% UrwtrdUnive~rsity, 194&2.
6. R. X. Gaoody, Q~ert.. J. Ivy'. qt. S&K., (6, IL5 (9ý2).
il "byr, lbtbods n? qplt Cekcuj~Amior, :mo Alauoe. :A-6471,Oct. .9&7
8.0. M. Fi&sv, 3. Opt. Sac. An W., 690 (1958).
o. . 3. Mos~. J. .'pt. *Kc. An. X0, a" 9.MO).
10 7. J .MhLa e . U. SbIv. J. 010t. Sc. Am., Y. 25i (1909).
1. . %. *r-mm, ' I.t . 8. Gla Pruc. M.D. S.*" U~a ObI State
1. V. b.hwtiet, *A. P. 0. V~=rv, Pk,.# &e A. 2~MA. 3.%ftyM
... . 7V. 34rollad WIJ A. ft*V. J. ar t. SQ.A.9 3 1059).
1T . X. T . ~ a . V Va~l' P . er.& a, A m. !An, "W).A
M.I erO 3mA. L . I ý. n. ft7-
:1 W~-'-%4N.Vý1sa as r" AY ot.A
20. J. I. 8$av, Bet., Report 6 tUoatmct A 19(604)-1003, Ike '.ie
21. S. 5. anmr ead D. Weber, J. Chm. ftys. a, 80 (1951).
22. N. V. Mpotte, ftys. Rev. :U 51y (1908•.
23. 1. L. Velob, P. Z. NtabLler, "A A. F. Lump, J. Own. lhfe. .1,
340 (1951).
2- . U. IVal"and SM. J. laaditowE, J. Ch. "hy. 20, 1&66 kl1952).
I 4A
Siiir
J • Ja
API'WD:X I
A ORPMTC1 EFFECTS
It is a well-known phenomenon that gases are adsorbed on the surfa'ssnf cont.ltilere. Because of the sampling procedure used in the presentstudy it was necesEc:-y to invertigate the possibility of samlling 'r-,,jwhich might ..- i•. at, a result of ouch adsorptior.
The absorber cincentistion w for a given sample was determined bymeasuring the partial pressure of the shentretn Sam. If ono. mould asumethat i neg!iZ.b',.e s.zunt of gas wa adsorbed y the cell windows, t,,tamuunt of absorbing gas traversed by infrard radiation would be givenny the prroAir of the c,,t length and the partial pressure of the gas,regardless of any alsorvtion on the cell wallA. However, when nitrogenis a-ded to a sample of absobing gas as was dnns In tha prosent !nnveOti-glon, the juestion arities as to how much Absorbing goo remins In theoptical I*Lh. It -.eem. 1;.-.vble that :!%e nltr-gen sight displace soieof the absorblng gas from the cell walls; thWe effect would iesult In agreater amount of absorbing gas In the nptical path.
Pon.=r an" Weber2l, in a study of infrared absorption by CO at bigbpressures, found that the CO concentration did Increase as nitrogen wasaIded ýo produc.o high .otal pressures. They attributed tat Increase toan aao.--ption-desorptlon" process in which CO was adsorbed on ta cellwa•ls &nd turn was iPlace" by NW2 whAh was addec2 later. The CO can-cnt-%t,•i: ti portio"c of the sample talke from the cell was determinedby Peimer mud Wite:'r with a east epsotrumeter.
Tn the preseuL a'.ucy 4.o Mao spectrometor wasevia• latlo to use tomonitor the absorber concentr'lon. Howevez, revis•L eneriments, weIchInvolved the three gases CO, ISO, 4aM C14 in the three dirre.ent at:ovp-tion -e1l1, ware performed in order to pin a better ýndsrssmadian ofswch &u adviJrMliui - dwer-ptiun prveuss and tW "eýxuie which samplingprocedures could be erptld to yield linrlws se&apling error. An a e-suit of these exqrleaots, along vw.th what is genirally known about ad-sorption, the following conclusions were ldq &nW the coirporendingsauplinnr ;, •ceoures were decided upons
(1) It was Tount' *- the adsorption was essentially eitepieta witain a pvn.4l %d a few secWs a:rAr tia absorbingpas had been added to en evacuated uell. Ts p]esamnon
was mhok#4 by di:ng a sau$.1: of absorbing ps (920, C0
an MU ý% t, a. mal '#hle asont,ýrou. the taisf-utl &Usuipuoaby the sample. The Infrared &Lourptioa was MYvir fouMee tndecresce signfIeently after the sample had bee:. adic.,thus Indlicating that no absorter was disappearing f-ra theriptical path as P result of slow adatrptIvA by the tellwalls. rule userIment, of course, did wet prove that therehad beers any Adsorptlen at all; 'jut .ias. adeorpUuo wasloflf1rrd t.v the neie. &xperlwv!ilt.
isR
(11) ra the second experivent, cow absorbing gas vas asddeto an Initially eawcuated rf~ll; N vas then added and anabsorption spectr-is, was obtained imudilatel~y. The samplevas allowed to remain In the cell end spectra ware recordfaperiodically for sevexal bourn or even days. in most casesthe Infrared absorption vas found to Increase, indicatingthat the amount of absorber in the optical path vas increau-Ing. This inlýr555se was found to take place rather s].Ovly;within a few sau.tLt~s only a lignat increase in Losorjpt Zlcwas observed, but after a few hou.rs the lacreamn ia absorp-Ulon sigbt correspond to as auch as a 10 to 20% Increase Iniabsorber coatoentratlon ina extirese caner. Because of tbeslowness with which the 'desorption" took place, the seqil-Ing error was sinimiaed by making a met oi runs within emshort a time Interval as was practical. In no case vandata wned whidaL wai* obtained from samples lett in the ab-sorption cell ovir night. In most case:c zaaplk's were notIn the absorption cell mare than two - three hours.
(i)IL to tv be expected that the relative emount of gasadsorbed and displaced by Ndecreases with Increasing par-tial pressure of the absorbing We. It Io k~oxm that theaamount of p. adsorbed Is ap~r*3iint~ly pro-w.-Uous! t p 5Aher p Ias the pressurs of the Ve %ad. as be a alue thatmaj uot be cosecant but Is always le8s than %.Alty, Thua,it is to *e expected that the fraction of t.M pe Ukat toO5lsarbi IsuAvass. vit... 1n=rtactng pressure. ?..lareultwas also caofirnad szperlsentelly is the preaset study: a"agligible increase Ia infrared absorption, It say at all,vas observed aflwr ad""g to *&ePI. bevies partial pram-sums of the abeortbi Ol pin a*"**a of Pofl.300 m Xg. ftegreatest relative increase was observe Ift the case of sasm"leto which tbe partial proeserve at the abo'sru betwee I sand10 za 8g. For thi .- aege %try Cow results are iaeluded whithlawolve saullse format by add~t il Wpt seqp~ae of abseftlagpa baving a partilm pressure ies" tian - or ý = Ed. Chrtabsorptiom tells. !1-55 co and 6.'¶ so) were ased Is Order toM-94le #$MIlNs Of loW ala..... i4"4 16~trttift withou. "INaG
,Aaesiwey Im partial pressure, of the absorbing pe.s
vt~ ~devblatim is ftquIre*A to meave the adsorbed gLtrue -AW dell Valls b? PM#in, a PMAnOMM a ll-kag by say-One ow hae Api~t wit) Mhlio- .'et *estaei. lwever, geset tbe reoults of the euprteriia.al cbecks 'f %Uip Abwoamne*e%.. vrtthy ofat llscuelva. A Lypluel eapilumi. sodS as esfull.%a: A asapt wvth ak 1rs-evr ,f epprouIestaly 1100 m 1of XgO mes put &a the c*e' and a1.PWe L& ýemala for a tuesibutes. The 2tl I IV- them Opened to the vganm pu" amAPMM3W. for aPpaoimtvl~Y 000 0iou'* afts- tbe Ymsae bedMeet. reduced Le. 0.1 so Ag. The valve to the call "a theeclosed and a opectirm of the 12M moclreginan waswdlate;lyosr*aaw with tas cell in tbo optica'. path- Ro &aanrptlour of
'Tt M- be fLa$ ~tW 6- wa -T-Lo
ehLI~ae ýa rl-w Idi jl- &dF a sd uuin
-. To"~ tmt=JZ:-. la fta-S mrLr".a MOLA o 21-1 wW. zf mb lx.,q~'*mI !Sitle 2.i
= 1-1a. .:~ 0" ;Yu 'ta qr-= ]a= a .mqr. 9
: * jw w.. at-Nrmr =ywe=
r,.t: ~ ~ ~ , -r -A n . '
4- 4%... *4C 1 A a.o - ý 40" -6 .
~?%~ ~ -. , i-mA.wt' -40h *-
-., A, Qý: uskot otwt Uni k.
vu 6w. ai.0 in t&tp.?q' to 'm ml.
which were formed by flI'Rt lntrodvi-Tg some N42 (say 20-30 mm Hg),thben addinR the ad~sorbinig gas, end finally more N2j L~j Lhe desiredpressure. It is po:;tusw~d t~hft. the tfIrnl. W2~ i'"-"ud1ed was suf-ficient tn form st Isyp.- ofv N, on the~ eel kwalls before thbt ab-sorbing gas vehs inc:-oe.uced. The azc-o-t of absorbing gas vhi,!;:wan adsorbed on the walis was apparently redu'!e!i because orthe presence of the M., layer on the cell wille.
Thie re@in1t Psogrsts thet the sam~plem should be forsad by add.Ing N2 befrt& the abembing gas, then by adding sure W2 to thedesired pressure. Al"4.ough i'. would still be lifficalt tv besure~, ore might expect that some absorting !&a vnul4 diop2.acesome N2 fram tae wall's, and the Laount of absoiblng Os In tkW.optical path would lecreave. Thiu method of forming the stapi- ab~s the dlssivantage that the partial. ;reqsure or the *bdorlbi,,,gas cannot be measured a: accurstmwlj when It is being ad4od toNL as when Lbs :e;.l Ic evacuated. Fur eamaple, If 11wereadded to a call to a pressure of Or. ma Mg *ad N..0 aided tothis until the pressure wao 105) = Hg, the partial pressure of3.ý0 (5 Me PC) zo"'4 Auk~ fA*t..'~aaair-telx as If the140 were adiled to a evacuated cel, anM the pressure measuredwith the abeolute pressure @mug..
The nothod elf SAddng N2. then tbe tbaorbing *a, and finally enVVN2. has the ftuther 4Ueadvantale thAt no spectral of the sample cau beot.tAin*4 for 'val~es of ;rvow-Aaw leses van lan pressure of the 12initiallyadded plusi the partial pressure of the aheorileg Va. Ihe tatal aheoup-*Irmo ft? &&ýMre sampls ?VMo Ay thls aet.h- Were :saVr*4 wit'; thosoof Vempkes believed to have tht some 'valias tr chsoottor elan"Netvotl"and lorwesure bult vtlIL Vora rurwa j ALroqW';1Q4 t"e start10ai IPP :the cel beftor the Ip vas added. if the soere. oplew vu formd t7sAdIn'g an J%,'In ti t. he "Ul ofter It %ad coon r.ushed witb -"eal puwmped Maly .va.Cfiulva.l: luag No. reuce 'Ae prve,:&;r* to opproalmley:a.aZ.O.i = V4, It Vae "o.~ tiat the agicemAt '.e tow. TUis seeItCu~t~s tUat a Ukyer of 11, .11I riinliwd on the n*ll walls after theasort pvwi ne persoa arA &arreL -A' rotue tup adsortiou at tus absorumse
Anotbier mothod us#d to eatimate tht amoos of sempling error arisingtrom *rto~eortav4."ct* who to 't~re speetra of sa001e Istwo different cells but with vxýaee of &V*.,rtar eaoiestenvtioh ed 2quIaie-lest treasone teloeve to be "Mtalt (WA~olvaleat Jrrwaev. to 4&fm4oa arw'1.. thil Zsoloa Go Fefbu~eii or example. UtO m1lot be G&We tothe I1.5$-0 o&I toea pOVeG#uf or .0 so Na. PIQ was then a*de 'V3 the6S.%%ur -112 to a 07*0surv of'C Ac I I.ftAC I . ma PC. It: %Mt' the-ad.*** to -ow?.~.~ eel I t.!tI -1 oitsivolefte Pim4U-tre - tho oea I-%tall.Q~La LAL vella Uves. "md Use *am abeortor eoweetratios evserm.for cbws I* the 6.15-me sell 6e to adeooptlon or daorptioa. ftim-ethe ahor letell cooetatme oalv 3-1). " error to th deteiralmtiao atI"n cesierr tow*e troltano *bas Iiarlae from ca&%rVtio cr Gmaeorpoafooreow of tMe abeorptioasepeetr of *twe- -wr .s se eevod to giveto iodleatioa of Mh ~w v e atof p~n~~opts wi4ch tilot plopo In
Us liC~ataaluag beth Vý **4 1
Samples of very small. absorber concentration for CO and N20 wereformed by ad~Uling to the cell mixtures containing a kuow fractior. c? Mr).sorbing gas (I '/10 or 1/50) !a W2. The aixtut.'. wer* ared in r. eri.tAnic It" aA44Ang M2 firet, an~d then thne proper amount of absorber (Co orN20) in order to reduce the adsorption of the absorber or~ '.he walls oftho tank. 'IMip mixture was formed at pressuree9 sufficienitly high so thatthne rela~tive error Ini measurirg the partial pressure of tne'absorbinggas was small. An electrtV-ally ~irive:! fan In the tank into used to in-cureuniform mixing.
A portion of the mixture was tzan admitted to the absorption cellaftler It had been flushed with W2 a&M evacuated. By this method it was;zissible to use samples having a partial preffenre of the absorbing ps
eq i týnfn~iý of R ". 'f Rg. without having to measure pressure#sle:3 that 5-10 as 17g. This procedure should Increase the accuracy ofsampling. Higher pressures were the~n obtainel by addIn& more 02 tot.mixture.
Bince the N~ was added to he* mixing tank first, and the cell wasflushed with 11ý fore seing evaeusaea, 'wa would expect on the basisof the previous discumsion that these costaineys voulA have a layer ofM2 on tte walXs which would tond to reduce the adsorption of the absorbirt: -as. Ofe wou&ld further expect that what adsorption did toks placewould o'cuir slowly after the Paopl, was admitted to the cell, amid thatany :'-%Wc :' the absorber concentration would be a decreaso. This tsin contra,., to toe expected Increase in absorber oe aseuatic causedby tt. .h tom. of ths avtefrtlow as by 1p when the absorbing Vawas Admitted first in the usua~l way. SWSISIl samplesf formed by omaiuasrmwere -"nfd with saIts vWtui' were believed to have the stom, 'altooof abeurber ^onenetrattom and liressure buat were formed by a~iing 1. tothe call after Uhe absorbing p wasa afkatte4. Teas cmpwarisoos erved"a ancLnor 1nliatlaon of tha aawuut of error bjY &Aio4pUo& or de.
It. hob"ld be notoi that the emperisats perforned wee i..wfttioiatto prows that the prucasses described above, ouch as the odsorptioa, the
disI~a-~'~.of ow as p Mn the Cell walls by aatasifr, the tormag of a!La,. ...' ;m gas, *U.~. aotualty oeccur Ia the mainer suagptesd. It ass
w:ybit *.-. "1 Uvov bapoee4 pi - eae om rosaswmbAls to view 91 van%it to be f-wod in the .&rAtmurr cos-trt~ng *4tarptia, a&" tht theywouk.d atcoust for the tmesa 19 of k69 many sampling oprwonate %biab werepe rf%-rA .
As 0 tvfs.' of U*ee owpriinats It oas be eaoslvede that. to st"lessuch as the P&Voent. .a., *0 aeff SAS taWOO to puuweat. eseesaie o"WpLiseerror Iren admorpiti.. oeftew. t to believed that, by W~futlvp tb#sempUo# proec.4.we )met 4oon,1be. ouwew to the detrtemition af tatalebsorptlc-3 arising tee. oftoptiooa effcts wore held to lisso tha twu
ur tme parnts% for samplesf having tk4 parttal paifesewam of the ashorstiogme gettabir them 50 =p 4P.ol V. ltes thea flee Port-sIto Perwes Up
PART B
ABSORPTION BY CARBON DIOXIDE
by
Darrel F. Burch. David Gryvuak
aww Dudley WUliams
iII
CONTENTS-PART B
PIP
Miat Or Vligove
A. V"", 13bs amarukm rosn
11. xmmi iS &As~ AM or anA. bf-k~rfttu 0Calsftert mt BUpvam~rt
z. Usfelowl"m of bm"b*a-kinlrw Uthoiqma in
0. bows "a Aoaw7
u.in. --m 3716 An* p we' *
xV. 1inz. 4. 00 nV. . mi 3aa As on Wn
A.. am*% st 20mw ft gout *inwuWas3
5. t V ?mp~f on hvtuon a
69
YU. aim Immuw
LIST OF FTIGURES- PART B
Abaorjptjou curves fr the 2'150 cu-1 a%buil1l.tmtraUM the error mrieivg "rar in theoptical pa*A of the mpectromintr.
2 Abunvytion eurves of the 3716 and 4609 CarlC02 bana.. U
3 Absorption eurwe of the 3716 mad %60 Wml C0bands. 12
4 S total aW.ptlam of Use 3716 =m1 C02 UMvermin euigalvalt .megur. 13
5 'Mw total abeorpticm at the 371A ~ CO. bandvermi abeoraer eameatration.
6 So trial aWMIUy of go 3609 M71 C%, WVerin eqaw 3*et jn..uze. 15
7 %v toWe absorfl.Jm :r =h -609 c- 1 =aUserw abac"Mr eancetratiom. 16
a I tow al emarpt at in 3716 am or) mm
C% %SWW ftt ablsoar Coineestz~s. 1910 MW %*#^I abborpuseas"M 3716 NA 3w0 Wa,
C14 £bolis eramreWe oft205 ~ ~~c. 8
U1 Absorption ,&e oaw ath %M 50 M' CQ* '-AM.
1) to tow tOWTberUM at us V330 or, 0% tudwI*~a qw~aleatt "teoawe.
it so totm& bboe"41Os at' the 8350 Gel COR Ina"IueaPW ebowu 4ant~attaf. 16
-rue at U0r-ve- M%?
16 Abs..pti. aw.o at twlo am 961 ft" C%
LIST OF FIGURES (CONT'D)-PART B
PIgur.* o. pg
17 Absorption curves of the In64 and 961 cut" COpbands and the 720-87. cu"i sub-region,
18 Absorption curves of the 1064 and 961 cma" C0Lbands for a ogven sample at various tempera-tures above ambient. 31
19 fte total absorption of the 1064 cm- 1 C% bandversus equivalent pressure. 33
20 The total absorption ot tho 1064 c" 1 C02 bandversus in part A; and versus vP'.130 In part P. 34
21 The total absorption of the 961 ce"l C02 bandversus equivlent pressure. 35
22 The total absorption of2 th 961 e'l, bandvru-- v in part A; and srsta vPe0'23, part D.
23 TYe rmture dspeftneo of tbs total absorption
of the 106l4 ad961 cm-IC% banads. 3
AI Absorptiou curves Of the 875.-495 em4- ('02 veOsm. 42
P5 Absorption curves of the e87,-1495 -"' CO nrtot. 43
SAbsorpttoe curve, of th 87-I95 0-k 4 C02 regio. 44
27 Meorptie gurve of U &75-4-95 o-' C02 stoe, L5
d6 Asorp~ion :umvs or tM *t5.evP aua -k-. rotn At
29 Absooeple turves of usaI-l i,-'9ý en', COR wegio.. 0
50 Abeorptlos curves ot tb 875-'p W e Me C 2 re10. 46
51 abecotptae eratv of uw 871.4SK cv) COp regon. 09
32 Abseor aon curves of 02 6eplets, at elevatedtoesnturee to the W7..3 resion. 50
slort. i
V. 55,
33 17,2-:4) am-1 versus P, ftr sa:,oo. 3t~. -X fV.
I St
5kl!Veu .,rv aiusvleo
M-11vare 9 fr M e.6Aoat" o
LIST OF FIGURUES (CONT'D)-PART BFigure No.
36 X(6;67-7?0 cm)versus Pý, for &AaMPIis Or O~alono. 55
37 1(667-7?0 ex-1) versus P. for varic-to -luesS-of v.
38 1(667-7^C co-') vezrus v Zor vsrious •luss ofP. 57
39 1(617-667 m-1) versus Pe tof samles or Co2aSloM. 58
40 1(616-667 amo") versus Ps for naious viluesof V. .59
hl !(617-667 c.m-) versus w fr'r vrloum vaues
of N. 60
2 1(5 45-617 cmri) verew P, for sampe,0 of co
1 (•-s6vT am-1) versus P* ot ms•ox ils1~010M. 613 545.6 ) vermus. P for varou va.
of V*.N4 (04•4.1.7 ft") Vermb P fot arr low veto*#
n45 1( - WI)l!l vesu n P'n l fo vrl ale
or v in the 'eft*-ham portlami A(495-545 ~am")vegeus v o threis vaajs. at Ve is the ribt-mad p~*'e.
S6 1 (01%7Pu 1 ( 61--6S7 on-),W. fT 100-07 W ).SMA I5-61T am-1 verus' tqerftbam tot taut
lifforen
ABSORPTIO% 1>Y CARPf N Dlr,3Ttbv
This report to tie areond of three to be .Publishad In the preier'1.research progrs., which involvcs the investIption of the infrared Wi-sorption by pieso occurring In the atmsphere. Included in this reportare the results of the Investiption of the absorption b-y CQý bends at3761 and 3609 cem 1 , St. 2q 5 0 e.-1, at lo64 ene c.16i carl mnd In the eye(--tral rieap from 875 - 1495 em-1. The first report1 (hereafter referredto bt! Report 1) in the Present progrna -.ontaina results of absorption
measurements of the following bands: 22224 corl N~O, 2143 ca-1 and14260 cas- CO; 4ana 3020 awl, 130 as- and 1550 ca-- ',U4. The third re-pgrt
2 , which will be ~eldthe Final Report, will include results *:t'the mesurements of other 520 bands and som Strong 120 bands as wallas a section dealing with the "relative broadening abilities* -vf ditfe~-eat eases. The aostents of tasse thrsO reports ane Intended to Suppl-mat searila work reported by Powerd, Burch, and VIilisa= 3 (hereafterreferred to as urn) which Iacl~ds mossuremmat* of ",, R-1 '!ýv sloi.r-mtion.
The work ýy Wwas limited to froqumeslne greater them approol-matelLJM 670 om'bfeee at tke Uistaticms of the 6Peetrmtaf. Giana larp parties of the absorptae by C02 Inthe 875 - 45euW- ntoooccurs at ftemonaies below 670O W.L, It seemd deestrale te 9st~ik t~heabeorption ia the eantti sectral region, 87% - k"9 cel by %he use ofapparatus 4sceloped Since the Wwork Vag comiete4. 1,I4ee extuadisthe epoe-s75 rsgI^% conmCi., it 6"w t4u bmavik~a wI*t the %Wy appantu-.to obtat i aborptlnu aeoA Wh arm cmvvtat more accursto eamInc1%^ke Peoples corrosp~ndin to *aorter paths.
opondin to W aurter pethe tian thA. - by POW were used In Itheimmsuptlpon of the a .@ticeGbj the seed. at r ~o. W".' *CA 9110 Ma-1.Th two sands at i end %!a&a o va wea e. j 4~ el ly minoriev#4itsne %a tt. askuy of us earft'. atmosphere; bovir. a amovedo
,?the absnwpklvý. 'j threse bands .6 5&t*6ro other roasm, ebwas to the a4vkv oft 1he emepboree ftf Other pisnoti eceftulolg tarrqauUstles of CC2 . Yor %Mes meeoe ah iecteUptilon of tlea. terAd wasiact.e4" is the prneat. reesearch prv~e
levvmi ene~rtm@4a* *kitb heftw"ne rvcsMly Isuv.ee OweMaeannoM 0f iA1e %UWfPUQM 6An iLtW 04`1601* * evosephrie C%2. Tftoosmasurate wiilt b of i 1d9 by the of IMIL1mate Ilk atipisese, We"-Oaa,eetvh mteiiteetlk MAd -qWm p 'r~ ot... TR "'Aer tv t.P*OPwt dbatOhtAIft4 toa 000# -uT'.rlwsU itr !s eevary %Q umderstes MO. ebeorr.
U" &ZJ 4ua &16 s.% Jt~I. It# M OWM So pan Wai~ gth.tstoseetus., sherbr partial prsosure. and taute p-~seare. It is bey"aUW% -tow pre"&% Asia will Nri"hem U&e haiWl of % aboeajiftto am
Iterwsl sthp Uwei paramtefW. iqw ~aff Is. as to earllar it.IM vilanef4tt br "Whe )t ehecaptiae Cuvrwe fahle.. evos. &A~
~. UMS, SDWOLB. AND DU3MLZor QIJA3TX?
Spectral. reg1ons siu frequencles ar0 tipf0IU0l t terz of .. 'with iwcitsa of ft-4 thrtjflt the present etudy, except In1 rafeNUCO toother work. All tabulated w1iaob of Vartial presure, p, total pmemmeP, and equivalent pressure, Pe, are expmsuaa In am Xg; end abOeorto path
use i~gY.4r. Volvin, fro %Adeb the syaofl #1 to u".
AI(v) 1. U.. ti* tam& maUuu1 &beurVUum et. freuomey v. whiba wouldbe o'beemte vith &a £isntjmmat *f larimite moasviag p~ir. A(w). Useobserved tvaetlom'. s0.owptl at W. daenfidu an the eve:tza.l out width%M4 is extreow~ ass a mctt~a P. as a T .a total atoorptict,ot as abuao*Uaa bead JA(w)dv to .pmalsd to JA vd A Isuiodeaboat oftbe spectra,- slit.vidth pewnidd ton Lmito or integration imhLti: thtam"1 hWM.
In eeetta III a qumaUty Dell" a o foti~ Up r tiosi
* A(V~v~d (1)
&AMI. Ma9 IL VWXAIIIR AMSAZ&ULMS aF rA
.vn 4.Iforoalt ia~rntr rv "0,4 to Obliate M Wown-patescm,~ Our th pmenot lametifkU... A PorU*a.E~r VA& It oqvIWs
'40h 446. Wh~IV01-.pae abiv~ript'on W,. Ae %"A -a. obsorpheS Pathsbotveet mOO ami WIO to. swrot. abooayuem tell& ot le~ous I-IS1MU.8 CS veo "eyespa Wito a Foru"i.4lin ~Ibo " epmtetamtr *lob%ma tacleAo. Isa %istim 'oak. All smpleo vrto eavesd at .gloa C%&low 3r of *Aifm"o v? COT M aid P2. itO WoeWVOO U4 to tooUeie.to m'ý at Ito tr Uf ohe ew1pit tells, eMd tUm utd a:61"eua.&nh4 the qteij ebeniptis fitm the ato"rpt' ovW* Vmu di0.
IN Ast mwryw-~'4Is to he Fto"Ot staip LAbOm**4'eQiet1Lr %v4U e% WeA 10 'IP fto,. 'petM1 MOgis ft&b a. Mtofrra SO as ft1l.iWt
W4and 961 Z&al baaiii, antl (iv) Lb. e~m -Ori~ue~on. It atisafo'r each of Ltrese spectra. mW-ons Vera cr~A&I~aw £eparat-ly ard =0~ 9V-suits are prcesent-4 I.i sections III. WV. V, ani WT. rset
Ea:!h (if these four spectral : orers a nm'her v1&7 spettralr~r-n It. ther.Tc~re -e-epre4 a4wunt&aPo,.aq t3 U:1vie eath regice I.BMaLler Pub-rwgio,. n.- t3 deterMIne **fth-r ltioý tnstokl mtt3rptl z- huuaais finctiona;. azrorptlon or eaý_b suib-reorton. It Is~ leeuiblw Lo dividetthe lar~er spectral r'egin'n' into almll aubti tewh a V% , L!
tte tot.al absorpt.ion detcrmine1 for e&:!. witi-r-gArm is virtuall Inds-
determined with LV~fnit?* revolivng( pwr. As mentioned earp~r, flubt--tA1 &bsorrtlznjA.w)dv of ~ ei.tle tand t".&5 be~r B'hYdt t4, ie Inmepend-t:- cf tte ~ ~-~,JIVwIl~ed Ulie i. no &D~or~tInr. bey**%the limits of Into .jtIýrt. It rollova Lh.at Ue total. absortUuzi of tmsub-regiwis -- !!I oe independent of spectral sl,1%Pvidth If they were d1-vided at frequen::~ca. vhts~vr "me was zero absorption. W~wever, It vt*:be seen In sections In! - jr that there are nj f-c~xiam .1t.~n tkielarger epectr'~l mreons at which Us.. shoorption is tero tor aaarkes, ý'vIng large values of v. To* -s thermforw necessary to choose optlmmfrequencepe, at whicti there was absorption. to boundaries betvaen .!:.a..b-rwuions sunh tivat the depn4.'vite of total atmoritilon of eamh 2ob-re-
zin as ',aast debm!uleaL r.n the sy-:trai sL~w-v1iitU.
If v is tb. i;~quewiy at. which ivo nub-reginow art divided, theobserved 1(v) just tj t.rw aide of v, is partially due to asitorpt~cr. atfreq'zencies slightly to the other side %ofr vit ae rwoolt of the ririt*speatral slit width 4w. "It touzrulary frequenciols verc caoen ci, Qttt~.o fractional absorption was virtually syInmtri-al. about vfor a~rIustely tu vavv nimbere en es:b s.i..a., vii i.e., the fra~ctomal abearp-tion w'-s nearly equal at. a C~van distance m *I ýXr sids of v,. If thefractional absorption Is eyminstrical about v, ni @.h->wba slitfiin*~ticn it also et 1-., one vt*.&I texec L U-_ tWL aboorptiun ofsub-rerionr AtvI4&A a' V -*_re-c l
?be ~:~ nC-..rmcz f..r :.;.% 104%1 Mnd 36C) W! bands werv.-141einto t."' **a~~~~.jonm with the division at !t' :',"iý orepnd u
~iinain absorptler. ~.4 '. t - ofi'ss In secttvm TTT the,. the rnbe~r;.-r *'t.- .- Ii~ .----; 41 iJa~w LC II
C".bh aide, thuse waking It. a a4a..frequency alt enicti to d:L*wldo thetwilm. 7* utol bi.irpt ion wasurel from Uhir prtioms of the abeorp-
Lim,& curvei at fr'equenclea greator than 56A0 cei ic referred 1.0 ma tm371 -1. lAnd;. a'14 trftt tin t.'- ",.!r~'~ ,f t1.'z lnterisal to
Ma~, PC, al- 9 6L ca - tbanda are *itmtlarly divided at 10W3 t~the ftvjupI Pi*y .JttitjA.TimiIln m~ ofll min =- Wr~ b.r n t"Is.~!For t!-x tareer -.axpl-' atu~ltel, the,~a~m abulorT' ton 418 not. 4*-
Best Available Copy
reached4 a &!&ALm& at approximatey 875 =-I, below which the ffactioA&labeozptlan 1ncreaese. The limto or the 961 csi hman were therqforeQkbsee to be 100 cerl MI 875 a-'.
WA 2350 corl band .&&iMa at IA. hand center and tbe wts' ab-inorptloa oa masc sile of this bowuiakry wu dateraiael. Mw tALi absorp-Mem, of %be e*4r* hand vas round by adding the valties of total abeorp-Unas of a*etwo porticas
Tbae wre sweserel steSs and me'a band. la the spectral realm. be-Wiees 875 -m 4" e*1 , the atevoeat bua" having Its cesear at 067 eirl.
Tb fts"Mtias evn4~aos6 to usa abaorpim, minimt we maoa temfor &U1 .simpea; sa t%%" rte~atnasmn tarare thrsue mt *%aisabie Ia
bwv~is besees tQs weub-relaa. So sajiux parties of the absempticsarieS Its. beads hWWjng Pr~dan 4 breMee b&O M fneeftaey oj MW"ebstvua ti nab" s "el breuhe tIa 6 P "t eensIaiW l.4 th !. for allsamlesi a"d Uat a .Ib";Llft *%.-. d-ee2ywevnic, euat% OA fre-vanne or asinsma &aheuetiam he a fW a I.. am *eka ike. - Ca e basinof the anase 4xnc~stus. It uee 4e~Iad" that tbhes~e "Sta the IA bAramhes,at 7M. 467. 617, "A %5j mr w.*aiAd hea" toe ba dares belos %fepitrol mab-regles ar ONt touve"9" es asa~s' aLs wL ~aytipuwasn 5UOsmsj.y awe at fr.Amsiee below lb" imrl, oad bapllwems t
f~siesq'e~a mT an a-lV% W f ettm as a part at 0 9 Gall*Wd 11 a?-h 4" ISeiMe was 40"aefw 41vided saw the hellalug
sWah-regits t I" Who ofas "Mayelasi 7xt Wi. GA7.1I 40.
m ~"" at" tretasus" ebmesplis. which to ralate the "atow ab-ttyptiss bY a. (1) few go"h at %MeeI esb-tagims to rel~u to
puwwu* .ud Fe, %T aew ~ ales IL' "Cume VI. ft WMty %meMAUW = Aftl 'usumt bAbovaerup.'me OWfum o mab
of t%* 04-rwe~sm. La oifh 7'-W ,a regift. a" s w me. a&&"a MUPS teWl' .ek ~ s .W , S£e#- - Mn esUau U00 NAS ON
Smam Aretuesel Obaeepueft fAW 00 interval r - veIs *VaLS W WIMteuete of so ve"UMl p" Is %bat latooval. M10% to .hmbed wer-
vied VAN IM14"; P14141101 Is ash 00 ar 6,li ft-qwetI.a
th ebseuptia. of a %&48& Slaw* or Ok end M Opurtliag6 ba hviaga ""a 4msw e eamse"Wumi to own to amon an go par k pres-*we p Of -as esamrt-t 04 VWl *Van U&e %WW betl esW r TusI s Lt a ""Itall %I& urn ti alf Wt ftau" e"Ultie at "ae inpa** 1*W14v*A Smoot. 1ý "a *Wa "at UObs W njwag tteeft oru ame @Mt "a ew som I&a "ee i o a O&Mea VWties ft" "aSolvaufts 14..ova Pe whish is 6o.1s "~t
P. - (11-9 a P(*5)
where B, the self-broadening coefficient, elan be deteruined e: k~rimentally.
Thbe value of B was determinedl by the method do-esxiNM in Report 1 tobe approximtely 1.30 for the CO, bands included in the present Ati-y.It was shown in Report 1 that tee value of 18 my be so.hievhat ~tf!,fern '.for different bandp of the seome pe; it my even be slightly c'lffereatfor dini~rent, frequencies within a given band. Although there my be.smill differeaces in the vaiue of B for different frequencips, the valueof 1.30 is believed to be correct to within t6 to 28% for virtually allportions 6f the bean" studied*.
By substituting the va1'.je R 3n into Eq. (2), one obtauins the'aollowing expreimr,±on for the equivalent pressure of the CO, - N2 esamples:
IsN + 0-3 0F-P~w2+i1.30P (3)
It is noted that no quantity defined to be equivalent pressure wesused by HB1. However, the quantity (P+n), which was called a "vaightedpressue", was used as a single parometer in the cern muiner that P* isused in the present study. Using (Pep) as ani equivalen,. pressure is,of course, the saw as using a value of B - 2, which is to be comparedwith the value of 1.30. The latter val-se Is based on rather carefulmeneovroents code w~cently and to In good agreement vw.U. theoretical pre-&ictiong bi two well-known taeorists, Lewie Kapl&An and William Benadict5Zdwarde in a recent study of the total abscrption of C02 bands used anezcpreesion for P. which is equivalent~ to the following:
Ps (P + p * 0.-; 92). (pressrwe In allzospheres)
I~.s expreesiua for P. is equivalent to using D - (2 + 0.5p), V. valuevbicL ia grcater Lbau that used In the present study .ir 'hy M13.
B. DE7CrI25I 0F DOUBIZ-MMNGM'3C=UqUU IN StUDMY OF STRONGAMUPWRICS BOWI
It ii. well known that, Vkhef L .,onventional -I~.nie-besa sgectroms,'iis employed with the optical path open to the atmosphere, there are aspe-LU&l rogivns over which the radiant power Incident on the detector ts nat-auced as a result of absorption by atmosphorc $&on It will be shown
*The Final Report will conitain core detailedInformation concerning the tlo.ý#,winatjon ofS in a nec tion devoted to the relative broaden-ie.q sbUttles of various names.
lbJ
that care must be taken in order to determine Lii. :or2*ct value of thefractional absorption A(li) of a sample at frequencies in a region ofateepbaric absorption. It will also be deownstrated that atmosphericabsorption within a doublo-beam spectrawlsr can giv rime to eri3r inthe ini~suremaet of the irrartional absorption of sow s~~.i ngtabl.yatmospberic p'... in order to demonstrate these phenomena the follow-Ing quautities are defined: E0fv) to the wradfltn -_war incident on theletnr'tnr with the sec~tremeter niet at frequency Y If there is no absorp-tion by the satosyberic &sses in the optical path. 'Ime paver k~v) in-eludes radiUition within tbe freqý-r;. interval 4a, passed cy the spe'r-trater slit. 5w spectral intensity distribution of the power 7t,j';ovet the Interval be depeude, of course, on the'spectral intensity 0.2-tn-1bution of the sourne as wel~l as upon the "slit. i'unction* of U*toeohe-traemter. In speotrcmwers such as the ones used in the present studythe inu--ensty of the source Is nearly nonotant ovr ar a~ nd the olautions-ter alit f'unction Is such that the intensitY' of Ro(w) changes graduallyover be with Lts a naum at frequaency Y.
If a sample Is placed in the bean and the radiant power inelident onthe deteatov ts reduced to IH(v), the fractiucal absorption A(y) of thesanple Is defined to be
A(v) i ov - A~)(4)r~o(v)
In the case of a sample for which V(v), the Live fractional absorp-tion as viewed with Inf~l~ite rt-solwing power, cheap* rapidly, It IsFnppareat that A(v) will depend on ths -.-.!ue of 4v and on the slit func-tion.
If frequency v occurs within an absorptiou band of one of the atmos-pheric pass present in the optical path, the radiant powr Inc%46nt, uponthe d~etector is reduced to MY( ). If the eummplai Zbvkn fractional ab-sorption A(v) is plý In the bea", the power -eacblng the detector israduaeti to R*(Y). ?bhe appartr fiactional absorption of ta~c nample AO(v)is then given by
06-) tAV *V
clare rnU-t 'ý, *R1Ctfl not to assume that A*( .. A(v). This obqualityis approximately valid in many cases; Mwevver, it haa been shown by 90that A*(v) <A(v) if the .1uple ceing studlied in the saw Age as 1...#
atmsphric~.. ~ %e ab .'_ption. The inequality Immdiatel.yabove cnb x I nnes tayway if one thinks r'f the radio-tion as having yassed through the atmospheric path before being ine.Went,on the~ osI~p]e vots. (Actually it does not matter whether the raftationpasses t.hrough the sample first, or last, but for the purpose of discussionit will bc considered as having passed through the sample. last.) Thie in-tensity of the radiation incident un the sample will not be constant asin the case of no, etmoe]V6,he.ic absorption, but it will have minima at fre-quer'cies crrp4'hn;ng to ithsorption lInes anti maxwtu at freqiencies be-tveszn the limes. Since the sample being studied is the same Oa as theatmospheric component giving rise to the abscrytion, the radiation Inci-dlent on the saxple, is greatest at froquiencios for which it e1.sm- '!a-and is least at frequencies for which it absorbs most. The not. resiultIs that the fraction A*(v) of the radistion absorbed by the samle isless then A(Y), the fractional absorption observed with no atmoaphericinterference.
It is apparent that If tUs swuslf being measured is different fre.the atmopheric pae cdlvin rise Wo the absorption, Ae(v) aigbt be greateror loes than A(v), "ainding wn tk.e relative positions of the absorptionlines of the sample and the atmospheric ps. If the absorption lines ofthe sample nappan to occur at frequencies between the lines of the atomo-pheric pa , A*( ) would 1, greter than A(.,).
rn a double-bemu "., of instrument such "s the Ferkin-8lmer Model21 used in the present I&rmalidation, error In also Introduced by theatmopheric pess* Ia tho optit,,l path when the absorption of C2 or LOeamples 1. being studied, Ouch an instrument records directly the ralilof tbe transmission of tho sample bean to the transmission of the refer-encei beam. If 1*(v) is the radiation powrer incident on the dol.attor frmithe reference boo, (l-A (v j Rilv) is the power Incident on U.: itectowfrom the sampl- W.ee vtbi~h has pasasil throýAef a nample laving 1"tationaltransmission A(v). The apparent fractional absorpition recorded by thedouble-beam instrumnt is
165
-ma :& Lur-m F.6 - nw A oowm V-=* U
tfft= we L -m -m -4.w %m zT~ -t. -a 5wwm-
IN ad me --k~ m rý ~ m
=a =. .rsa an afaoo ffffnamo amf~~ war-
art~ -- mm U a,.... MO M MOZ & =s ;i&a TML 3W- md
4*f mg =wm - w=*iW-.
m an I& w p ? -om - 3 Z.6 =f .zt. a L
z; So. Odr r- "a*-a..m* ,m21ý1
l 40P 3= imi 10*mk
~~mw7" 2S27 ORIL" It a -LPi i..iv
.Lym =r- vwp .. z w= ý =b 6N A3 m
ow-m opv nU w t. e10Atý lkamfcm A
0
V~A/2 W4 0z.0 2 2) Pe 7 4 0 I
I B0
A - OPTICAL PATH OPENz 60[ TO ATMOSPHEREuiV 6- OPTICAL PATH FLUSHED
WITH N?CL 80[
_
2250 2-300 2 35)0 2400 2450WAVENUMBER in cm-'
I. kswmiption em-mok tf"r the 2350 ea" -C, br .4 ..he *?rrr silsing from sir in the opti .iI V'atI of the
3p~trewr. The absorter concontrall.n of tne savil lw iaprniwastzly iji,*-tblrd so grtat ps the abporver cic'entra-
txsnI mf the CO, Ink tiU ma~he path cj, the va~m~l beafn.
I11. EXIMI.MENTL E"ULTS FOR THE5716 AND 6o09 ,l CO2 WnS
Tracings of many of the absorption curies for Uwe 3716 and YQP .m"!bands of C ,N otr shown in Figs. 2 and 3 with the :pectral slit-width in-,catesd in the over left-hand portion :! Fi.e, 3. '%a rt-.1rl dashedline at 5660 eta" represento the bout.dart, betwen tho *o'nds".
The Jata are tabulated :, 7%00- 1, which includes thv va_-ee ofabsorber concentration v and eq-ialeit pressure P. for each sample aswell as numbers of the .igures In which many of the absorption -cvarai;n:a. ý-c Includi.d ara rewnr".. %Aa ;u s...,.lLluu ur the sampleand +he valur- qf totl absorption of each of the two bands along withtheir sum. The vslw. of the sun of the total aýsorptiono of two bandais included for emparison with data ryored by HE and for the con-venience of other workers who treat these two separate bands as one.The temperatures of the samls, which were near room temperature andvaried by approiately zh degrees C, were not included mince the totalabsorption of these two bands varies onl slightly with temperatures.
%epresentative data for the 3716 c-I band are plotted In Fig. li,where the different curves corresponding to various valups of v relabsUm total absorption to ",. A qualitative *xp;iALU st oUn ?wa~xeof curves ouch as those In Fig. 4, a well as of other figares In tiserepo't. was gven in Report I a&. will not be repeated.
In order w sbow the dependence of total absorption on absorber con-centrstion, vas of absorber eoceantmrton wer taken from the curvesof Fig. 4 and uted to obAln the "smoothed" curves of 141. 5, where eachUurwe correspond• to a peen vallu o k. The o rem asurementsof the 50 is" band are presented in a similar asnoer in 71@e. 6 &M7.
In Fig. A is s*bow. the e•u ot the total abeorptione of t.a two bendplotted aginst P for various values of w. The solid curves are basedon data obtalned In the present Investtgial , thile the dashed curvesarc b•sed on 11d ,sta whieb a&& shown for coprison. Tahe figure per-ait a direct cosparison of the present esoulta with the earlier workfor vulue. of X = 4a.7I4 and 9.W8 atmos om. If ova were to InterpolAtebetween LW. .vo c.-rves cornms.ptiAng to ý. and 6.08 at=@. as for valu,of P* between approalmatty =O0 and lO1V i Mg to determine value. oftotal absorption czrdporAInC to X a 4.7Te Ats- ce, one would find thatthese values differed biy appuroxInt1 5 to 10% from oalues aon fromtheeuve corre'pondtng to a1.74 ca n from the WW Ukt&. Simllarly the9.48 a-zn: cm curve ts seen to occur close to where one would expect Itto be relatpie to tb:se for 6.08 and 12.7. It eow&d be noted that theOW d a used Ir the comparison represent the sml.lest saples invooti-•jate.1. N;. WLvIW une Would expuct the experimental error tj 'te tht Smat-%.%t. Tue estimated trror In the M resultsa wall a.. the jrs&nt re-
,u~,Is ftpyr'o:rW~e y e*5%j thus, MWnearmoiehv1* tjnaf +here it ftt.iy
168
ISt I I I I I I I I
V- 2
I ..- ..8,- ." ........
SE -
4t 0 d
L __ ___ _ 1 p1____._9
",I -o E cr Ln -"• "C "" r--• C' w 'n E •J
,*- qt r ,• ,D • , E V0-2
0d66660o -L1I- , ..J ._L. _ . . ,..~ .. L ..J...._,..I I__
0 o 0 0 0 0 0 o 0
NOlid8OSBV 1N30HI;I
ISO
C 0E Ci~ ~cn-0Oq0 0-
U ~0
0 10
0E
- 0
rE, f( to~ fn rn 0 0
rL c,qa
.:)Ld~~S8~ NJDC3
ITD
0 \ \ i ' "I,.\ \ \ ,w
iaI
EA A
-0
N I"III- _-a
0 0 ,
S.... •' I I "1 I I I ~i I •Iq Il
00
I-ot P A
UcI
it.
9--I-I %\\ \.\et V
* \\\
0000 *
-L- a I A CA--0 0,
ve.
1710
4ooC02 (2.7p REGWN) ion,,
N6 cm-- 3609mr . - --- ...-- . "•2"S43: -"..-,-*"_ 6.082
I,.'"....,.- ,. - + .-.-- .. - 13 .
-40 9 .- - . '--- "
4.7431
"A- 0,164
40 '
K) 40 -00 400 MoPe in mm Hg
1,19" •, .ot" A;. V'z'rP ''=o ow ON ... . am ... .. *%we,felw **•%4 l, - r•. 1t 0 .e *'A eao.r ".1 %:e.: .•.,•...•.- ~ l .tl I I •',• * U4W@tll~llll ..lm WI *lfYi4
wiLIset ý:'to, .;a~r2 t.re .* n~.':t MCI* f*~ -zzo
:aIe3'i.t~a± .oo '1. A, -'l =c 1ko "a '-::
"~qutvsaIen -- reesw.-f Iniijzatcd. :iv -Interpolating net-men ..me "-orw f,:IA .- ,- pvv'I'býc .iLermv1s -n1e 'ý>c&L .¶bsurptm of .n. a1. nd
'609 .-c- :anan for namptes fer whl..n Mea valice of v and P &ae n.LW~ad ny the zuresg.
th ",Z ab~iorp-tiOn to *U ra=NA w"an r~e' &though-tAhe'wLaame *-AaI .... lUat*@.L$ Do detel"2=n: ~rz.Sf aczr.=a.. r.-= zues :tazn &A a ~n .aFig 9. Twto different eulrlcai equatIona of thls sort mi*& :'.v =Ad by.'{B for this band: o** for vaJ~ma or total absorption greater 'baa 50 co'rad mact'-: :'r a.Il_,r -!%1-"a. =a e5qu~tica 1atseJ.ad fzr $ULU Ulu"a
czampls, the &mad~inm- pressurr of wftlb -do. lees tftha 5l0 =rug. 1bmy ofthe-9= sample u in tbe P sajL Invintig-ttion ytold*d vwalussor ztota_ b,sorption- loss theA& 50L Clef' as6._ ts10equLVl~wt MPiruMe Of ths.,e sLe SO-I
varied1 frro g ft ew-ummH to impyroztevy 13"A uwfg. SL=a the, pmessedsam -yre~wit r~re%%er raa~m of -and %, and'Vines' the'eqVIvaletjMpmisuw. used in: the- prwesent study- is: b*lie w to ow. more- AU*LtbX* tftathe. 'veii.atood pzwesurse used :y SW, It ased ddestuib3a to, ryiase'the-empirical equation- to be- used for -vauesm ot kata4 nbsorptlon les, them
It was demesnatUtd In Report 1 Mhat nn equatIon o'f the foiw
vue -.uwfui. *cr -mu.L& va.juss of Al v)4,, nnd tftt theL %(alaeeof ther Coup3ata ft.1anmd b could be easily dsta*.NjS@&gzallbjCall 18- ~ozftw-0o fe-termanW- tte- viltw of the- euprltal cooatmat ftý vallmes ortotaL aboorp.tica wer: :,55: fm.in the- curres of'FIX. 8 for dLMfegvulumeaof'Pand plotted apdist W,ýL- Dffermt 'veluse ota ,vmote'* tf~.aM tia
.Jwq Atrurvwg Produced rnv usinw, 0--.65 am skmmw- in rizi. * . Mae -uzr S 8t~ws*Olecd uiW'e in 114. 10* the- flwv entre corrie~p A tt!
P., < 760 = 1% amv rnarly ooln*1danb tar a&Lase uf 9'oftL ebm0e,tt*s be-tiW-50 ant )G ca.1
* 3LnL%* rU.&O. rmtc - t0-ft-owwwg lqm-mellcomincaont It As apporent thbat UN ew- vI%&-4. -- ~cpesd~
rk z-J ~ toe Z .-_ @ =."c L VV,.*, roir the. Va1.ms .tVaaLo~tat .'3aorotlo- MVWpresetld. Portione Of scow of, the curves or Fil. "o'Ore _!t 4d to prevent 1ut~F'-?V4*45nx Iomwelp Points Lre &M, ali to
ý et~tIone of tL. .r-es.
:7r
st 14ý,lnCOPY
I0
I0 \W'\ \\,j C
0 c
L lk
LDL
C'K\
0 r~rF Ij UAP(A)V
177
___ ___ ___ ___ ___ 0
400
000000E EQ) C\\t 0 o55C
c¶I.I4 0
79 u
Maus, if #is Iioluteil to Less than 250 so 119, values Of tot6 tboorptionbetween 10 and 50 W.4 ctut be expressed us a function of VP, rlaceboth the ordinate and IoW abocissA of Fig. 10 are I.earithsadc, t~a Mliie~of b for Eq. (6) vas dateir.ne4 from the slope of the single straigbitlice hiahc) bast fitted the points cor~zeuponding to the values of totalabaoiptf -m W. equivaleut prost-te specified. The valve of b vw. foundto be 0.5$.
On the healis of the above diseusaica the following eupirlool equa-tiovn and its zvgtos of validity vere derivd for thu 3716 end 3609 cW1
JA(v~dv - 3.5 vPe C-6510-58
for
?t<% 25 we us,
amd
10 4fA(VMd !o =m11
It eas too moet for 20 - F <, c'%o = X if 30 < JA(v)dle < 50 *a".
Wle &M~rIzal Sq.LWC co" be coearsd vift the eorespoodio eoque-?z1*ft frow PM9. ftiech It is 10oftn&.1 tLt vP14CO!
I'Wdv-34 (Ftp)
The auto* orfig1. 10 whiet conwes;4@4 to hipar squIvatoat pno-cwtv, coul~d P, thifle to the &Mtf. n oade to occur ul-,ner to UPurv.0 .Irmep~owltad to l.ower £w..uwe.. by usiWS am ev~dw~s 0 for P
owIertban Uw vwm!i t f . 1 wI r was tw .. 3Ommp. ft ?0 au%%iPeqva "s wo, sd, the curvve :Prrespnd~tid to tti. !?'J ;ameau:-e wVM14
o@Uf to. the lot 1L of end above 'A& e'.rwa of Lever inraeas - 41 fur )Aqprva1't.. of -"hI &bwV~tcA. %us Ow Coeeluiz '*ht "au '. al bew'p-tic. twot, be toecrihed %I a tweetle of w -4 ftr I~rV wvm. . P*amd swil values of V. ThIs Mul.a was Aiteveed to *Coe 40=1 t
;*ol e M Re coaftnod I theU preset Iawesl~ttes. It Is pttaktn 14ies Uy lislt Il tow 'w mrc** of whit, of jA(~ veGf a-A I*i eas~1
Oq eUM :. j'r "916 Aifemtt¶ Values Vrea ow =. ceah i fed eefte* 0"eut~ntw Vbich VOMIA 0austefeetuly nI*1;1tJ'")iV to V m . fur all1.46 6 . V~p.DttM.. :% Ilk 4s1at thet several sk"It V Ol4 UOnw.etearv. eewl Uth* "tih wmid be %slid o34 over wry Witted maupe
4 ~ r I.t~O4 and',. It A14 hort so" s.,rt.,vI* to dertee as
way equautions 6s vould be neceasa~y; and it is recomended that thecurves of Fig. 9 be used for value* ef A~v)dv( 50 ce1 for uhicla Sq.'7$0 not suited.
IV. &WUDMVI. REM"~ FOR WI;250 eftl ';0 RMN
Traclage of many of the a"aorptc.n curves of the 2350 ra- C02 be.Mare shown LiFigs 11and 12. Mhe dta aealistedin Tale2 ain a ame
;;zU rz t usel 1.a Til 1. Dkforc wau~4U o al isorpaocf tAic sper.trua, ii. vat divided lao two port-asns at 2350 =7 , wAn thetotal absorption ofit"ech portion vas than deterninad. Yamus, of totaLseeoz,r'4Aw o' eAch .Kirtion are g~ven in Table 2 e&IW with %he tin oftheme val,.ae., "bF"h rwproeatst the total absorption of the entire band.U-m the results far thc *tvw pm'4=8or*mi not amalywid sepc~rately inthe present sb~y, they are tabulated for possibhle fturee u~s b7 others.
Ispeiteal.tlve data art prisenatmIA Fisg. 1) vhare tUs total .baorp-tUes of %we entire beAl for varsous values of aheorbez oceost~ratties toplotwe eadList equivalent Preessure. noe solid Curiee awe "eaet a" &&bObtaLoseI in tVs present investdation. Use 0!shs4 curve represes" Ogdata cormspoadia to h~ &Vw ates to so*-% to occur slightly asielm it*solid -mmre correpoodit W to' 99 &%wes tamr values orfPa betAs..epProatma*ly W M4 anD O 11 . The %&LVes Of Wttal Gb*MOzptio ndi-catud by te 4. 7 &Vwe ca atm.# are sra~imat'1y u to (4 greater then,o"e veu.IA predlot mthe beast at thue u-.l1' cwu..e. Motr X results,vblcb ear~iact shin, ver. comwex end tu;ad to te Lear than M~ 'ý!nrest?"as eCo"VespeeU re*%L iu In ihe phrtstt sumly. 21 est~mm arrwis%kG IM M416114 a& VeLL as MAI Preejet res&Ats 1s Ib%,NitWy t%. SW,a"8 eoae4mme thAL %he W"%e.t '*tw'.. twe ea.rl1.Vrk wam %% Proasnweat to vIt~ia In Wks!c it %VariresTwe f1t~Ie or veiwee or vand e erased A b6U.a LaeeOUSMaUGa AS I& L ee "WOf %U 3716.G awL
ý64. bweo. %in AW reaulto whIA %mtr cjaqated vitb the paeowt,esi~ite rwepet~t4 tbs somlew ý. leastI atsorber coamemtatlm, (seme
VaW e M>&% t%0JA %* 9&pW e.ws vaFqi i O W 4MUt.
to wto4e6 IUe i.wifa of( Ti4 4A, výwa t--ial St~b&AaLIUM Is %Qotvtg1aeat sakeobor uea"ei~ttiam. by Iniatrolaiing bt-OW4 WA *zese Itts Poestiau to tow.mla. the tatal abop~mOf a wMini .eml. for whichthe Vatusa nt I ~ ?%It acew WMIthnW us n coves by Fig. Ill.
ZAL.4 iJ &ak.& t a. 4*#4Ir"a "WueU VW WrIvA to rWAla VSLU&*q1 ':'. ateosptlft ieea Uses N' m& I V SOt F n crier %* darIwe
aw' .. P'i i6 rtlationship fea the OWLks 2mwes for %itab tse m1,,
Ia
-7- -7
0i E
rv,
r$-T~--- vn*, -- T P -
~ I
list
-Jill
Ii 7-
4L0 0
-4 L
ciC5. c i N__t____
Lý32
X0o~\ ~ --N
jo
ODa
C~ (M
CY
A AA
000 0
- ~~ ptI ~
\~ \2Il U
"" 1 s.
\\* \
I-wo A A.v
X f
Ii'r
I'09a.-
U .-
7~
Ti~.
c~C
*.J n A- (M4
184 ý8
0lz
o'f r-otal al.9orjptlou are loes than SO cWir. vu..2 .7r* 1m 'Licorvos 'r' Pig. 11% and ie' I#t~d In FIX. '45 apt~ wP d.'
of th~e !&I ~a constazt, j.7 uv-s dt*rL**-t to .... smmasr as to%is* ofa *T g U. Piz" 1ýhl flitare the teaý r~g eigmation was dafrlwd
.- !!' ~ ,3 r~ a 3j I1 nd fA4,4v tried.
1->.,j [wh. '448
10 < F~ 250 ma X
K~ustlon lo : also valid for
10 ýc -C T(ca-:
15 <fA(v)dw < 50 cml
V. r"Onamt. MIy=U 7 M10" AND 961. sm - M
?-s',218~s of rvstml' absorption comes of the 106k and 961 eelbarbs are shown t~i ?1@*. 16, 1T, 01~ those 1 Pi's.F 16 WA IS comepamAto :=4-0s, eaimisi. as or C02 uilussi, w9"l0 Q's. eurs ". Fig. JL? Oem-sp',nI to #sq100 OCUO~SUMza of CEla WA X2- 24 abSOrPtIOU cur" OrFlit. 17 wortszetended to aweximutelY TO or&; who ft em. .1% f hi£ nna or those ooreon betmmui 875 and 730 ad aim disouseed La Umemf* eettloo. So abosovptlon cvem aIn FIX. 28 1FWree3 uwa Stanmope
a.od a 10t vIonos tw"Istarth above ambleu; Q* sdaultI oif ftema, a sU wel" aother obtAI1e4 f re' samples at eloataed Semperato79Lo3 3 djecossed aear the "n of UL'19 station.
it i. seen tree fnss. IS aid 17 that the abeorpua It statutlaI1seyc At syproximtsly 11.5 caI for evem the largestsm. 3¶ 11 01A matthe hands overlap with an absorption minimum near 2 l'O theInv. fivjwummy side of tat bead. avotber absorption Uniamo wogew at
STS n'L Uwvertical dashed imues at 1000 clm4 ad "~ cem- FIjp.16-18 mrQo5.nI. the toniatmdres between the bwAds xhis were Adin .-vt'ilid DetOGUO I i
18op
I - S
Ul 4W Ap
48 !\ '~20r\) 520
'NA 102 962
10.t 9 10
w'0 \395 V
w ~ ~ 9 vttt of¶w~ l I.pHmSO,
so- 384 260
I mm
00
- 1245421
8 0 1 - --- 5 - . ..2 9.2 45 3120
40 r -
20w in ( :77 "
) 40 cm\I305 033
60" 505 032
209435 30?08 2045 1780
-945 324 -
O0 '--•--- -L--- ! • -f
atmost'O0j
4 0 .m mk .. .H g . _ ,%
6Go 222I80~l- 5 !30~ hi I" .
100--• 1 . --80.,,00 900 80C 700
WW'ENULN8R in an-'
Iof tt 1%& &M
0%tw o"%A Ig& ' I*.
I
0 OD-
•E it ii
NIn Ii .... /..' I"
• .• i.
°I, il
tI,
|I
Sk3~l)q
Sodta for the 106 .an 9k: al be&f are sham in Sh3. 5.luck Incues~ the sampe towntpaz, tote asaet 0.5 &are" ý.~ am
vwU US h Pummwtmrs LUste in ftbiss I &"it 0- f "Jeejq!CO& - 3ldxtuvo are Lima Su s those be"an, Iabosbmtr Math lonSUt.of 3M0 ca.
It 141 nsauo lit U btL- tetl sh.xies, cc Ska &CY sl *1 M7,ban to craj~ 1. 4..~W~ t c tngzen ; It gem*gft". an**&&"to cormet trima "aa o tota sabaipuent^b thes m Liontue. %&value at %*Wa abaouIt.Ia of all Us sape* ast~eda moo re tmqkbtwo~ Vast -jusstYS t: 2N~, vIeb mu *uqc~nstaly Me emiNO 1mms-t%". 50u MoCaa6zy owaretloa men dationmA tiM 4W laftZmtesgiven war Us s of Skis sattn toosersin. Qo I sat fbte aude
Is Vkrt A at Pig. 19, w tle Alsa ft teboark~myl of is apg@f Csow ean *Lop~tus soklS re toViat Sb R L we. uGemaPod toe a alS gath Ioa*o V to Sbupftin PI.Wstm. tore. Is p, UOft Pag orn4 tetal aserpasto a.us. PJotAW &vim% ue,
bet s" eaw- .emorp I giees imubw styj ". lefteu.
value o mawteS tros %W omu of Rig. 19 to ~0e asb uat 14. so, Za pan A as tow- oafterus ve #Lemol 0.wat13 frwthe &tffetn% m1" ý#C V "5Ce". ftet a me U0140@ to AmnOntome =SWOuMmhP tetWe tow abohreat am 00 "Simt~as .Leib*?q Stu %SL of tup SWeAS14 smalet V" ftet~odMS is, so n
moras for Pie. W0 ALL of *A poksom abams :, 8Lt I at Pie. 30Va'. ob"Lod ftawm beam S~t ore IfS4 lj a" I.t is *oft us% a "*glenv"e ftae proivt sel U SkI the pi ew cnwpoalag t is Sb lmmtfen
V"Im r1P*- From in--r fto olisnAso .qmla te ine 41 SM4a1%0 USAalte va)J114 vwn *Doom% for me too 400 he
furI *.is) fo.a. n`
IMIcaga utlr W s o L9a tw"&om Wru
03 W 0%bassis o. P 00 po It o ese t Smt a t P4.
U)
I--(U
Fn *1
I-. l1-4* fl-r i I -
LC~ -I - sIht!"
ti, 0 1
Ir lil I I
~~~ v J -5
'2o U p()O
006 10
IWE Z
18
S-1 IT
\ 10
Et-
1 . Vv
ILL
* CL?
clA
3030
(D \- 0L~ I
10
c - ~ IF.
0- J_ _ _ _ _8
I-~ I ;aSry-T -iIIIITI
0
.,L , , V4 f
IV
was derived mAn its limit. uf va.Lidity vere det~reiznes for the n~l W-1CO2 bend:
fA'vYtdv . 0.016 Ev,0.02510-78 (10)
for
1 < fA(v)dv < 35 ca"
100 < , ('160 ma g
A. WEE! OF WDAM7Oil TL AISBOOUO
In orftr to obtain LACsimatie an tUs tagprstnre dep.eaftne ofthe total absorption, absorption camwe van recosdile fox .6AWw iifftrant sets of samles at leparatuause above sakIet. A tbermnstor weplace4 26se eacend of the Cell "n a temprature diffleresce b~te~n thesake was found to aidet. fthi difference we approxesmteo1 -CfIateqatuses near w*Iest and Inc rveaed to appwowiintely Ikk for teuie-tweve near 75ft. Th tempve ue tabu~lote4 I% 74119 3 If an aevnsatgeothe twic to the nearest O.5'C- It was sot possible to kialo the absorptioncall.
Abeorpti'js c~amvs curreapooling to com of the sets of asaplte Is-vsetlgate at differeut te~mprtures ane &bass In Fig. 121 and the MRe-tiema4 abeolptiou is V'ee r.0 &%oo. V~h tempernatre 6% a"A treqie-at**. Values at total abonwptiton t.'r both 1)u4s are plotted apkinot
ntomprtn Is parts A ad S of Pig. 3). Soe otawe of parts A end Ito well aw parts C ant D ane discmseed below Is fistaindolg a quantliks-Uv e relationship betweca total abeuyptifia OMd 0pertaufl.
Awn ane severa~l fact*" iee mhigh t coakv4.ut to t%*fhug Eijtatal sbaorptoem with temperture. Own or uaeae lactors lavolt*s "Inlollslou ejtrasiciey or %,.% etVeewttnt univowleo, Afeb Is proportionalto lbo slie heif W14th 0. to he a" In a wibth wrstwo Is bountedto emaulbute oal4 a minor part of the inareas, is ttb abeorptloo v51*temperture ofta two beab rAder considuration. Xid sellst to basedas the 1..5t tht the total absorption of the it)O ftl t; band. as well-40 'tUer ttARAMOS bk"**, ineleasee only GILetiy) with W-Vtfe wee&An oav wosAt not aspct too %alf-width or Mae Uses of wweC Uonitlaeinco more reIS4. oILU Weapeter them the Usnes tr tather CQ&
bthoutet y, the Aet Imoreast factor *oatribatieg to the Is*reeIs %otel alnoryttoa with te~mprture is Inettase Is to pupalatisa of
195
- ~ 1~VMV
\\ j:~ Alb.20 40us
-vS N N - 2e~ -
'Bell ~ %. .L C .
J L
Ul AP~tQW
the lower vibrational. energy state iving rise to the absorpuon. Anotherless important factor Is the rccdiý,rlbtuon of thb population of tbe rota-tijl energy leveli, aseociatea vith the lover vibrational statL. .)ne
would expect tast, the latter rector would result in a change in the *tapeof the band, 'out its effect on the total absorption would be small In com-
aralsEn with the effect of the change in population of the lover vibra-tional energ s•.te.
The lover uibrational states of the 1064 ci"l band and the 961 cm..bend ar dsimated by (02o0) and (1000), respectively. Their energylevuls are 1256 um- 1 a&d 1588 "1 abovs the ero-point ener-v level (0000).
am qumtity r(s) to define as the fraction of the moleeules cf aDoltumman ga• in the curg state Ei at temperatuie 6 (in OX). if E, Isthe onera above the zero-point o"erar level of on3 uf the lower vibra-temal stavese Involved In the present investigation, ad 01 and 9 artwo tmertuive near roou temperature, it can be ahovn that the follov-Ing e*qiomolon to approx~mately true:
If am asems that an Increase in the pepulatlon of the lowerenrr state by Increased temperature prou•ueb the seem effect at thetotal absorption es the saw relative Increase In absorber eonceatratIonV at ealasmat tmratume, it follows from Kq. (i1) that an effeetiwvcoornea. rati we can be .ound by
bm v,, e v At. tWeltusv R,. On the bse of Is.(12" .m would ex-peat 'at eqeflmrentaly dteulinwd values of log v•,V) .4mld Yile6 aosrtmai i.IM Al pat .iPJLa •pin AL tat - 1/0). Vleie 0J. wrv were as-t-rolne4 frm the data end the stgps•t4 'mtrvwa I.Intt4 In tho nlloilngIMRAs r.
i'a t.' eur• in Part A ou F.l1- 2n eorespWUnr4 to w - Se o I[twem, or.2 :-.2s that a ttnel absorption of Mt)f cW, for the aXJ Ge I bendcorueepoemi ti a *w-verature of 26,3C, anda total absorpt~ion of 23.b 0*
197
corre.spamd to a tagerature of 36oC. Frm the arve in Fig. 20 me -e@!hae i a absorptioca of 2D.0 l• end 23.4 cil correipond to vafe aI'sVP' eual to 8800 sad r,900, zeupectivrwy. 'he acteal vaUe CZ' t•.-is not Important, but the apparent effective concentration Is Increai oy10 900/8800 w 1.2k. Similar caualations were uAe for h6, 56, 66, eM766 7 ad .for tae .-urvee correapaning to v - 1385 mA 290 M oo ea. Ueratio vejw 1 basted on ve a v at 26C for aAl curves@. M calculatedvalues of ve/v fcr the three aifferet sets of @Mle a ere plottso inpart C of PAg. 23 1n the innner uggeeted above.
Owe iee that the points in p•r; C u" Fig. 23 form a set1•1t lime,wlthi ex~pected esq i---.mu" error, and it vu fomd that en effectiveeboarber concentration can be calculated by the followig e*umtica:
We0 V v4 e1195 (1/299-.1/6)] '. (13)
vwhe th factor (1950) was determined from te slope of the line inpert C of T11. 23.
Sma . •r calculatloni were mae for Vhe 961 wl bead; calculatedvalues nf wve/ e plotted in rt•D•of 114. 23. fro• • ailoe of theiwe, 1i vas ro va=& T e eizectIve aborber oancuatrat1io for the96.1 =71 bend is given by
The *xperinrntally dett-sizod cenetents, and e 20th, Is &pi. (13)and (14) can be oam ,rea vita RI/k f ,,.. (11). ZI tOw esmry value1286 un.-, viaob coreesponds the 1D06 ar 1 beand, te eubela• ted torI, in 1k. (Ui). ae obtes" 180 in ONeiULIm wlik the eritLuldatmdarmn vwue of 1990. btailarly. It l" er1 ie embeWtioel I&J4. (11), am ob"I amne -I&•,ce. ecn vim ae e• UMv• t l t•,w-alned veau of 2%0 ftr the 961 W" benA. Ia vin of the seltomus& and th poseable eaperlsmtA erro, tUle egint Is aplt ged.(e then iocludes that the depadeae of totaL eberption oa theei ' hotbenad" en t .everee am b egwreovatly eqlAaekaas the Nw1a of emincrease In eff9ctive absorber eeemoatratic.ie Ib i p to p rtto•1l W IeInaree" In th populaticn of th Aer vlbetlaiml eslawe.
Oa the buts of thi eowe lsoiaam, oae wQd eqect that N-a. (9) eat(10) coual be uset to predict the tota abeorptI• a of 0013. At tNeM-turei beteen 2•OC and "100 by uulw,.1btin ftr w the value of ve frofti. (1.3) or (1h) reqectively.
R. CVrAM U OF•.•? ¢ IT MULM
WrU T=~ 0F EWARD
Z er.6 h r-eently pbllshed results of masuremente of totAl
absorption :! several C0 bands at temperatures from sabient up t*139001. Vae seauglp for v1hih Udwarda masured the total aboorptioa ofthe 1064 and 9'± ce bands cct 4asd relatively mall value of v; thetotal sbooeption for tim sample- at rom temperature as therefore @sellad the umoertealty ms rather larp. he equivalent pressures of may
o1 the sepls laveetiptd by Ihards urs considerably hiohr thenth mea vaiue of 3000 - IS used in the present study; therefore,there ae only a few of hMe eesults vhlioh 0a" be onipeed direotly viththose ot the present study. The total abeorzptlos of thve seailea wlehcould be onpared were in meat cIaeb syt•roiiately 50 to 10% lose thenthe values pred-latel for these sesiple. on the beals of the ourves toFPip. 20 sod 2 Iven thli large dGfer•s•ce vu vitin thw experea•talunert•inty I•ire* the total absorptions being measurd v wie small.
%a srsuis of tameraures cowered by the two investiptime of the10& end 961 l band wvan so lifferuet that the resulte could not becompa~red.
Mvar also Investigptd the • a' 1 aheorption by the oter CO&bsewe sovered is the present study. ls resulta fr the 875-495 Wa"rerAoa vlU be cnred to the present results in the •aet section. Theresults or the 571T50 3a 1 beuel Usaad %ane 2350 ear band ecold mt
e coared since tbi total ateorpUou of the malest sampA studIedby LIwards vs appro.imtuly , eq--1 to that of the larpet eagle used Inth2 present study.
V7. IMWOLML PMOWP~1875 - 1.95 W* - 51K5A1 =IZON
,U 675 493 ou" spe-ctral region woe divided lato five sub-regiohefor ose puzpase of maijis. Tmraings of ma of the absorption esum
ane ehova is Pip. 21. - V2; the suames or 71g. W eorrespnud to samplesot 02 aloe at variove tereratur*6 stavbusabes., Alte toorptlesceee."a the USOther fipwres 3onespoed to Imples m" sibi'ent tespers.-tire. U epeotaal sit-width ladleted at variout freq•-•ie *#aPig. 21. applies to the ateorptlon oaa-ves iu Pip. 21.. 25, Ad 26, Uiahvan, Obainva with 'he Ydsl 99 peotrusater; vWhle the sputral slit-vidtl indicated is Fig. $1 applied to the absorption curve to Pip. 27-32vhich wone obtained witAtho Mk.sd. 21 speeanoter.
The date axe presented to Table 4, which inalkd.. tw Vela1u of themean frctiosal atoorpT l-t) for eacb sapetzal sub-emoe as wel
190
o = ;002Roin
20 "tnO cmM I! 6,1
~ 82.5
40i0
re20 'w=0.046j mm inqotmos cm
157:~40 385;
00
w ro 0. 1'8 Pe in
310
401700 650 600
WAVENUMBER in cm-1Fig. t. t ,toie-ar%*a ovZ Uwi 8t5.45 m-t Coý vegjoa. Vu
ape', eIt-VIAthe Irleated Is the lover peorto at %scf &s'rt ftu to Jw owns in neg. 04146.
200
�-.,
1 �I
-- I --
�t�ZZZ-II I4 -�
I -
- - J J�-�' -
-
I -- - -
'p � �
Sp
_____- t-- �dJr �- -I
S* � -
- a It4.
I -
L . 1- I
-�I -
I' .1
- - -
- £ I a i � � i !'VOLLd8'SS �
20 fs604
0. 0.14 11
I2 I \\ 76
w i, I
Ii ii
20-I
4(4. imimc
t ' 'mr~
w= 5.7 Peii
r ... 2.,OP,4"il
4 0F,'f Lrm Hg
6O-50.2I 63.6
i1 ' 04 m
~60
,o 6 3000
4b.4
<• 60 lo
,L w al-5r in m m H., t-C.20 -o,•o
.
WAVENJWR in cm"
nl- ,' 9,- A% Ir I-l, -,-k
-f---- F '- 'i co F.-
~ IF
-1C
C".. e.,
it c~~(
NO' itiSO ~INK182
°t.I
' II F10[ 4
Iiw in 3e illw in' F in atmos cm mm Hq
- 30 atmos cm mm Hg j0.0,7 .0 029 0.39 0.15 0.39p 0.48 0.65 0.24 0.65
i 0.7T 1.04 0.36 0.90u)' 40 1.44 •?* 069 IR24 .78 3. 1.15 3.3o4.55 6.18 2.32 6.24
H,- II, i
,, IiX 50 i 1 ,i
6CIii ,
8O(' 700 600 700 60OWAV,.FNUMBER Ii cm'
Fill. n9. Abeorptllo carve er th•p 8i -', of cm % ft-*
205
�PI% �&
- es--.-- V
-� - E
- T= - ,-� � *1
- h-'.- I- I
V
h
- -� I--- -
-�
-- -
�A.
-- ' --. -
20-\( '[untmos cm\'IT H9
86'1 ý6 h
tk)L22860j 4 -
0 1 -----
Qr 40 atmos c:YI mm Hg-
o [3.8.o 30m~ 383I00
80 t54~520- .1
I. 1 1: 520
.0 0 t~ CV
eo 219
50 ~ ~ U 75 00 $0 0 550 300
WAVENUMBEUi in cm-'
?4.g. 111. AbaorpU" cw~v of Oa -~ &Mk cel ras. ThuGPGCMl OU.VtOWM lldleW4 La tW pa.ta fum nogunami to~ *ur" *a vilp. t?-*p.
0 " I
A Pe z 329: P: G.5w in mm Hg mm Hg A I
4 atrncs of 't32Cial 32.5 i:L TEP cm \\for " for Iii /r
<.K 32.5 C 23.5 \c -9D A ,R R I, ;'. ,, 23.5 C \
- - . . .. .119 .. .. . -- 4. . _~ 4 .•" I . _ . --0.5 119
-T - i~ /l!I TF HP w-, 1 :qt C'61"
4. 40 tmos 'mm Ha ,I IPA -,- .I
() '7" -_ I',+•'
S4 65.b -/,
U- ..... ' P - wa2470 P, -84b:._ N'. 3Otmos cm :,mm A*.
L C
too -4 8 .5 "• " !
•nkt" _"2_. , ".\\, .. :
1O5 Eton 700 600 540WAVENUMBKR in cm-'
;. . Aheriam vwwo eem.&e at ,a*iyto temprwktgr aIn~~o- t1h~.9 1 ggas
208
In the care of sa'ples having small value of w, t. major portion of theabsorption occurd near the strong fundaenuAl b.and at 6•7 _-l,
In F19. 33 a.re plotted •ix curves, eacrz correspunding to a d.±fferentabsorboer roth lengtbh which relat- &('2.--7 cm") to 12 fo -8-72 CM•J ,f
CO2 aloki. It Is noted tort -Ua values cr A(%l-vL,) ;hich are L:'..Figs. 33-4 have bean corrccted to a te=*rature of 260 C by usu -f thecurves of j' wh. , ch relate the increase In X(vi-v 2 ) to temperature.
1(720-875 CM- 1 ) was plotted against Pe in Fig. 34, where eich curveeoe,.jw1.~u to a. give-an<us ur w " as cte The x'a corresponA. to.samples of CO2 alone and the 9'z to samples forced by addiug 12 týo theCO2 sample. The triangles on each ourjv correspond to values taken fromthe r'Arvel of Fig. 33; these v2alue were obtained *by first .alculatinzfor each cell path length the value of re wh..a• corre5 i re, to th viluesof w listed on the curves of FPI. 34. The values of A(7W"-75 cvl)corr;sponding to the ealculuted v&Zus of PC were then determined fronFg. 33 and plotted in F1U. 34, By ving Lhe a .values represented by thetriefglen in Fig. 34 it was possible to exte. many of the curves overconsiderably ,ider ranges of values of PC. The meta -f samples vith YLess than 11.5 attos cm t.vkdd have bean formed by starting vithi ema•l
ej~unt ofCC~in *he 3.'u-ca cell wuA' Se'otn.S N2 to obtai~n the requiredv.alue of Pa. 'ds prorm,"-ire was aot followed l.nce the initial partialpressure of M2 for each sample would. have been t", 1-v fc." aecura'emeasra'eut. urtha; orrvr might also oris. prA adanrý tin of L% onthe cell walls; a pLen•mnon hich .' more serious at low pressures endwhich vas discuaed in emu detail in A~ppAd I uf Report 1.
The two curves in Fig )4 correspondlm to v a j7)0 ea, 295 a&oo carepresent samples C38-ChI, which were investigate4 by use of the MoHdel 21with a NkC prism. 'The oUs4 ..uzyee reprosent bcailhm investigated ty useof a Or prismp w±i.h ubicP. It wes :-:cessety to ust' larger spectral *1!-t-widths.
The alump of 1(710-i15 ce"1 ) for the MaCl data.. ,st of wbich isnot represented la 1U. A'h sinec it would result in ove•crowing of theelurs, were compared vith valueb p:edicted on too basis of the BIr data.In =at cases the 4iffterece vea less then -f wit" only a few valuesdirter1,.-, by as man an 8%. 1Abe cAiureraes w.e belloed to be due chieflyto experimental errors, a.t to Uifleivaces #41sing fromp differ ing sictralslit-widths.
Values nf i(720-M5 c6-A) waere obtaid4 from the oarvoa of P44. 3Iand were pjlteed in fig. 55 eaginst, v for tn', a:ifvres, v, "s of P. Jin-
Cw" -,aw., and tbt polats which voe a sed to determine the"e cumve were"V t,.A LU Vder that vLaue aomd be reao from Uo uuj'veoy nr- tsetLily
-W- -- Uas -te -ri or thec..:Y zpv777asub-Fagions beU6 .d~etermawi .±usCR vl-v) tro
TT-~
SiN
00 \ Uc'J -- 0
",[ o I0 8NN
0\0u
"( 0\\o
0 "C
210
1 0 0 C50 0 oi 1010
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0 00
00
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%v I
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0.
2112
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[ ' \ \\* '
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0
10
104- 0
+O I0I0
coj,+ K' '
113
10
cc lT-T~~ 00
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~ ' ' ' \0ki ~ ' !
0\ w
M,,
Nl vi 4
0 0
com~w~
214%\ \ Ib
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0 0 90
00-o Wol.0~215
[ I
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004
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o C6 JEV
3151
i*II I ' F~ •0I T ' -- I 'i
'n11 tc o OD
0 0 64
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14.14
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FL x',,,\, \
L 0-c,., , . -, .,••• .L Z
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-13
K IC
a.4K '
L) en
0tWO~j
22:
Cun.es correspoLulug Lu huse iu Fgad. 33, 314, and 5 were drawnfor the other ce=,-tral cub-regions andi are skoIn Fiii~ . 36 - 4:. Fefigure vas drawn for the 495 - 545 cm-1 interval vhibh relnted 1(495545 (%-!) to P. for aemple, of CO., aInno, cince only the samples (,flarge I produced a measurable aounnt of absorption.
A. EFYT OF radWW.TM (XNUN FRACYTOIAT. ADSORM.niN
Several of the .1n.tptLion curves obtained for samples at elevated+Pveer--t.ires are Rhenw In 14r. 10; mand Ith re!e!lte f- ** there~
L; iivur ir ,.c A lu'lle '4. Only samyles of CM ln wr nveasat;,ed, the pressures of the samples were chocked a. *the varioustemperatures and were fOand to increase seesntially a- for a perfectVs. The absorptlva curves for the samples at elevated temperaturesvere found to be erratic in the vicinity of the W5 - i r = 1 1 sub-re-gion; "nI theje por'l.on vr = :uc- were therefore omitted fro Fig.52. The excessive scatter in the data my have been caused by the watervapor In the spectrometer, whose temperature increased as the absorption
aell was heated, or by temperature gadienta vithin the spectroter.!t Is also poisible that the amplifier pin- ws not sufficientl highfor the recoMer pen 0 respond troperly. Regardless of the cause, theresults for this spectral seb-egion were muoh less consistent thenthose for the r.minder of the absorption cur.n,, arAi re omItted inmoing ariatyxLs.
'Me waen frtetlori'l absorption of each -- the other ?ow 1i4WL.4Is plotted aglast temperature In Fig. 46. Ie man fractional absorp-tion, of all four intervals Increase with t'mpere•r•e. No attemptswere made to ccare the observed increase in absorption to predictionsbased on the changes It population of certain energv levels. Two ormore braws m .n.trbAto to .he absorption in say of the seetral sub-regions,and a simple cbsculatlou semb as that made In conneetion with the l1amd 961 cIba nd• ev.A no' -. msla. Detilled theoretical ealculatloisof the oftect of temperature variation oan te aboorption by C02 In theIM • 49 ce•' region have been mec by several tivesti•tors Includain
3. COWARISOR C? MItTS VWMFMlOUSWMVE
N~e W report contalns the resuets of measurement of total a.rorp-IU, - ,.' samp.eo of am0 i ZOON Mtures in the A•5 - . as'
mae f rut approximtely I to 900 atA a, end the rMe•stu ca" e eca-aged vith the esul" of %Me Present invetoiptioa. It Is not possible
to orMar the total absorption or man fractioeel absorptIon of tschS,-.regi9 esince onl te total absorption of the en tr rete 5to listed
223
i'C* -I
S[ ar 0\ \.) vI- I -~-SL,-4 .
.4..
in the HBW report. Value@ of toti.1 prees3urt P e.vl CO2 partlal piensamup from 'Use O~W LanI wexv twc W calcuiA~e tone v,.ue of equivalent pres-sure P for each sample by use of Eq. (3). Thir value of P. along V~ththe Y;I;Uo v1' vas used w1Alh the. curvet; of -'igs. !.5. 38 141, 144, ar-m a,ta predict the man fractio~nal ataorption, Vroduced by each asample in6ach of the five mb-.cgiions. The total absorption of jaech sub-radionwas thea calcul&atd fromt the mean fractional %bborption by use of Eq.(I)i thea total aibsorption of the entire region van than found by addingup the results for each or the five oub-rC,1',no. Thl.; value of totalabsorption, which asa predicted for each easplet on the basis of thepresent work, vat compared with the -value obtained by MW.
The samples having the smallest abet. bar tPonaentratioai shoved thegreatest deviation between predicted value of total absorption and thatobserved by M3W. this Is a result which one eight expect since the CO2partial pressure, whieh is proportionsA to v, wine too low to be measuredet~urtel~y in tha MW etudy. Errors in the det'vraination of v an a Te-
sUlt of adsorption e. UO0 on the 061ll walls also contribute gr;eater role.tive error in the predic ied values of total abkorp.Uon for samples con-taining a low C02 ;artial pressure (seet Ampendix 1: Report 1). Uncer-tai~nty In the position of the sorc. absorption curv also contributesgreater relative error in the measurement of total absorptton of sampL..zof small v whose total absorption ir e!All.
Other than the fact that the largest deviations were aviivwdatodwith sue.'i.ex producing low total absorption, there was no apparent corre-latior, betw-en the deviation .4either of the paraefters v, or Pa. Thprvdicteci values of i-otsl abscrytton averagsd approxisatl~y i.4~ leessthbz tte *obeerved values; ;.r~x plienow'non could ar'ise frm a it nuber or'things, such as systematic exrore In sampling, errors In calibratl nsof the spectrometers, errors; ti the positionrv"g of the rero-abrorptionctrveR etc.
The root-meen-square deviation was found to be typroidmately 9%,
a result which ladicates Lbs v* i21b(LAB!. .. ýw !... th: =F"-1 -c1 .somewhat large. for the 875 - 140c, cm-1 bard (15-micron) than for thaother beonds.
5he data reported by dvrj6for the 15-mlcron C% absorption in-aJiud !~6 samples at ambient tempersture, whose valivee cf w and P* over-lap thc.je cover~6 In the inesent study. TMe values o'f v, P: *"A~ fnldvaxdsl sceplo Y"e ues ed with the curves ;rescntefi in this Pectionof this report, In the 30a= ranner at vat lone for the 312 datA, to pre-JiuL the total absurptxt.a oi each oamqile. With the oxneptl-t of thesample proe'. ImA the least total abeorption, for which the , ediotedtotal absor, ticnn was 9.70 erwate' toern t". ct)etrved value. the deviat..ono4Stwoon predicted and -ibserved values vas less than 5%. The predictedivalute averaged approwimatoly 3% g-reeter than the obaserred vanLue; thisr.4.Lt covilI be partiailly explairted by the faot that the Edwards result.
vore obtainad wltb masmes e at. 2O40V~ vh 4 1. the pvoeent AMt& were ottalred
ST •&K, i: ne preal.cted values hed been corrected to 294"K, thedeviatioo would iave Deon even less; witbh Ue exception of the c00sample the amLium deviat" = wwal have beez, 2 praiX32tly 3 t--' .1,the average diviation would iave been very -m1l. Thus, one concludes"Vhat the .grmmt is extrne2ly good and is ,ell Uwithin the estimatedexperiental er.'..
The Edwards latea and the HOW data provided check- f- tL6 amlesof the present study which have intermediate values of v; but no dte¢we' avave f leb to comre with the mallest and largest values. It_hould also be noted that te -4n4-- ,%lur of equivalent measure, as
d.vne ned by 1q. (3) for the Mwarda data, wee 385 me J- .
V 11 BA.D
1.; ass demonstman In Report 1 that under certain conditions theband Intensity Jkr(v)d.v of an amorption band, where k(v) is the absorbercoefficient, can be deteuined .rom curves relating the total abaxtiocto abeorber -e'trationk. The total akosorption fur sa~aee for ifhiobk',v; v < < I for all frequencies, is related to %he bend Intensity by
A~~v- v ik(v)*# (15)
Me coaitions for the vuali.Ldty of Eq. (1i) correspond to Lighpressures and -1l values of v. For sufficienutly Lig pressures mudaual values of w, it folloai fr- Sq. (15) that curves such " thounsin FU-. 5, for which the lc,, of JA(v')dv is p.Iotten against the log of v,sh.ouLd be linea with a l.--p- cf u-ity. The value Qf.riA(v ca. tenbe determined direvtly from the 1iniaz Priun of t-e curves.
In the prmeset a '"'y,, few.. if Bny, of the aemples had Pressuressufficiently high m values of w suffic :2•stly smll so that the simplelinear relp-lonshlp •gven by 3q.--(15) van coenletely valid. However. it
-=- - tz arr~azcaae. to simalar veluq- of v t"ere vrtodIng to the largest valiue Of P. m i - 5 san in the carormepMcL.. figures!'--rth ztm b--,. r=U- Ot. .d.r b L,"s v we I L wuern presible to estimate the values of bend intensn-j: ,, jv)dv-. The
eatrapolated curves were based on the fact that the aloleG of the curvesincrease with decreasing!I to a aba.uue val '-i o-f unity, end' it - 1i'o curves -e;pseutng different values of Pe tend -zo uoMva.,.
It. it rec-•-!ed that vs u~e, rr mean fr'r-wtionmal e_•+~ Ar-,)
ruther then otal mbsorptln m . iere dtermined f: t. sub-rzelonuin L'e 875-1,95 mrl reion. rert+ in oner Lo dpt.rnine the in-
226
ofA~v)W v from reatjigs of A(v,-v^.) for tho A17 - 667 c-i -nd. 667720 c*- sub-regions from pigs- u'and 38 respectively. The absozptionby the 667 em" 1 band Is l1wited to these two sub-regions for vi• -K"V and P. represented by poq-wtious o the curves used tM determdk* Oteband intensity. Kaplan and Eggers0 have found 4! !.--• a small portion ofthe absorption in the two sub-zegions g•ven above arises from weak bandsother than the f,,-A =tal band whose center ocrlrs at 667 eme". Th'value of band intensity for the 667 cm-1 band therefore includes a smallcontribution not due to the fundamental.
Mhe intensities of the other bands in the 875 - 495 ol" region)whose pr-Minent Q-branahes are seen in Figs. 25 - 32, were not determinedbecin--ue of overlapping of the different bands. The intensities of twoof these banae have been determined from high-resolution spectra byKosttovski and Kaplan 9 .
Because of the ertrapolation which "ae in."!-ed in Itesrmning thevalues of band intensities, the wcertainty is approxmately 20 to 25%,and is soewkat greater than ror the results given in Report 1. If thedeteraination of band intensities had been the pzimary rather than asecondary purpose of the present investiation, higher pressures wouldhave been use& and more emphasis would have beer put on samples of smallw.
The .alues of band lnterialLy which vwre deutrained In the presentinvestigation are listed in Table 5, alone, with the results of otherworkers for c•mparison.
V-11. sBMPY
The work covered' In the present repart has dealt with the r.Oraredabsorption of carbon dioxide, an! i3 i.atrmlu as a Piuykleimnt to earlierwork. Sawples consisting of carbon dioxide alone, and in binary wdx-tr-?s with nitrogen, have been inveatipgted over wide ranges of absorberccn~eentre•ton v and total pressure P. Fro the absorption by each bandnr saretral !n-erval, It vas possible to detezrie either the total ab-sorptlonfA(v)dv or the man fractional absor•tion 71(v1 ..v . _j uu
-.-_�. C.. cz. az r a- p- re 4luh uh uw the %Oa aLbsor'option of the C02ba ndp t 3716, 3609p, 230, 1064, and 961 €." for various values of ab--r!iw ..... :eiow --. a ftnction of equivalent pressure P?,, whioh Is
a parnmst., !.h1t includes the total pyresu4w I and. semal i tItonalterm ;ruportionaw to thes partial 1m- ve- of tho,bo .borbin a,.. Similarmetp ouf curves ror t•b vub-regions in the 8,5-B',5 c"L region were drawn÷.i.' , -,' a-n fracat•."l abno-eption an a f•mc.tion of Pe
A.•kctie.x :et of ('urves shows the total absorptinn of each ba"d andthe , frnctlonal absorptiou " each spectisi suo-r4lon for various
227
I I L M -: ' I I I i''iii~~,
equivalent prteasures as a iunction of' 4brorotr~eon Tiesc~urves provide. a means Ae' ;i*4ict±a~g total alusorption c'r mean rtl4.absorption for ar-, -lues oý w and Fincluded in the .ride Mrgne of theserararnetp.ra 1'e- In the stu~dy. it vas also possible to obtain empiri .crll equetticr bi'., ' total absorptio= to v and P,. !'or certainlintmied Nalues of ý, I absorption JA(v~dvd and iuivalt pressure P..
kbaorptiOL cu2 ves -.7or the 1.064. and. 961 um-1 bands as vel.1 as fortne 8,11" CM 91 i-fl, were. ra-.nAied for different samples of C(2
u. I1Tw-nnlp from vzrier.,. to cipproxlimatelY 7OCC. Ilie eff'ects ofjý.k-:'xtnurF or, Lhe lh-ýptuor vere iliuatrated' by thc .,eOf grenphs.
u.; f.~ ound that f'or the: temp !A re range covered it is Possibi. topr-dict. aw -Jc eaae ain to~tal at,--,"~on of the 1064 &ana 96i. cm- 1 buxndznov A: ,I -r. ýUPi.e.,ry fuyclion vhlca is based on t!. calculated in-
* In port.. in i*r*f the lever enanry iLcve2 gI Wing i-.e to the absorp-ion,.
EA,::i ý4bles vi.;.± include all the CO2 aosorption data are prt-sented at. tne end of the repo'rt far the use of owhe, invntlen~tmrr vb'Žmy be intereslý-d -Ir an awii.ysist different from thin': Fiven in the preseiALreport.
1. ii hoo- e prre~n r-ultn v!'.! be useful to 1-1-, 14!-tors 4Lo tre tnveri~s+Ad in the many types of atmospheric studies involv-Ir~g tb- nbsorptionl atne emi~eiorn of infrared rftdiattcn by carbon d-loxide.
228
W% ~ ~ ~ Ulk eA 1- co- - g ' j U
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I P
dl 44 §o4f Il ,!4~1,11;
C; e --- t 6c
sv'0A t 0I M1 -0 Otom an 4%do
o~ c40
0 -4
40n 0 -s
*,vlfi 0~.I-~UI. pdh* ^a e0 Illgo R C 01
mzz 9 *pU
.. 4-4
235
-*. C 0 U " .40. 0 C.O~' '*
~%a8 .4%* (Y.*¶ Vk! f-0* 0
j 4
Som
00C~C00000 00000 0000~ 04.
~tJ~b~t~t ~ *'9~V.St' t'O). u UV
t- -0C9i W"0 W4%'( 0D* L%0 W y%
- -4. C M
30000 0 *W000 000W0W.A4 *%% IE% 4Vf %
ft* F4P. Q w a o~ % 1 $*t1j at %t t L23
1-4-
A ('4
tR
Ai(%
stv i Ja; fI
. .ý . t .i I
CIS w- I "I
V6 C4 aIN
ci c d 6 ; 4;a d ý c;S ciC it ;' ,. 1 C, C
5-X 4 iti
3: .5 -- 5
O0 I4V 0'0
0ý 110hlo 10- Al^ 1 %~-. Ww 10 Q, 0
5 .. . . ." - ' - - %r.. n-.i il . -.
19 toCo 10A . t wo "a
~~~~~~~~. . .. .. .. . ... . . .. . .... ..~ ~ l • I ii • • I. .
.. .. . . .. . .. W.NIIN
1, ,,. n, •N S,,: . . . . . . . . . . . . . . . . . ..* ,19
.Z4-
N
N N N N N N
8 1-. 8 6. *' 8 ..4 It -
440 0 4'. --,
-- a .4 ,r
- nn0 N4 MN
V V NPI 4r~t t z
*240'
-41
cu 'i!;40 i D ChC
44 -r. 4 CA? OF'44C
44% 4 %
44*4
omVo SIM -. AM o d
U oCa.. ý^w-.- O
VAC 0 gn~0C uCd d44 dod A ri d d Cd; u
1.41
ý.V M CA !%--
rlrE F YCho~~ -N-Bf-
~0 a
.41;
'4 IL 0. 4 14 ft- t i 04 A N,0 11
I1*) 1;I ;1 tlibf1
* ~ ~~ ~~ .4 .(4'00. .N O (.r ' . . . *Z'Z . *4 0 VD
*iIAQ GAVS A04M &Roa 04a4.
2424
. ~ 1JA~'O I -
C4 17 1NC EM 4 9 96
b:AS
:37"
*~ 7'
egg~~., O~.~-, ')O%*CJ 1'jl~ . .-w sot"
it4 -0 a a I
mtzrwl 3... T
Table 4.. (Cout'd)
O w sp l e f i g . T e m p . w Va r eNO. No. C.- cieg (autos (mm 49) i(720-R75 cm 4
Path !ength 5M as0
c 26 17 25.0 303 =3 20.a x 10-2 Apectra of laws.C2"t 25.0 305 a6 24J. bc 26 - ch w.c 28 17 25.0 305 3 ~ 2b.0 obtai~n" In Comma-C 29 25.0 "35 'IC7 29-1 tmict bththe In-c 3-1 17 25.0 305 3070 35.5 vestigatlon or t*w
C02 tat"-A 161Cprism was uas" a"
'ber 670 WlcOU L s14wnk be Invesiateda.
c 3j 17 15.0 465 790 3oo Ua giv-o es ta 1 17 5.0 615 3M9 36.6 fnsleu..C
C 35 17 W5. 5O N -,,1'2 34 1? 25.0 1245 3= 40.x
C 38 I7 "50 .15 1700 51.3C 39 17 15.0 145 32W 53.0
c It 17 25.0 5730 1**A G E~.4C 61 '! n5.0 5 IN 330 &- - -
C 42 Ii 05.0 UMN 'Moc ?i.'
Z 44
Toble Budk Inteomtites
M. Valmue of jk(v)dv amW In umInts of mow,1 onri S.?.?.. values g~esfor Us proeat @tuft c,)ml.md to a Utfo..mtum of G0 , M t~GNUtem d umert*Jtlem am jzdieoated.
PiesOM stay ~a10
yrt .aL S rAvor 39
Pygaist no ft %
prozeat GV40 O.0i5 *0. 010
pro~ stjr 0.@ co 0. 006
Piesel S~ 30 I90
Umftao .to 170 A,WO&% MA $&"own A
A? --n)-63.'~ptyslr?: vleovaeb Dirietcrat., kir lbueerb o....Deve1agwt Cmawd. Nauseam Field. bodfow4, Mhaaacmart.
AP 19(&A)-H533, Goeg"Iues floseare D~asetarate. Alt kMserck
PNpip No 4-o, GA% Ai P,,Y" Om*'i4p hMoseb Owner (M95). On
*.law!& Up- Doputmost a.! lmto..lar, Mass. Udt. or Tw.eb
* - Mws .1. C%%. - e. Aa ý **~*
-. rv4; -I*1.*.*04- 11.
-j . .- a.,. :,, r. gbr. 4. rt" ne I.r In
U vow &w.I&a. WA S. 5.t Pe. J. Zbo. ft !2, We 19C
0. . Twv.. %*S 1. Zbaroo. *Q8cU.us ~a at ~ 3. Uo Xnao M.I.. -oat-oo ;n"140q WNW.' to ithaws ?:y of imp ?tome ttml~
PART C
ABSORPTION BY WATER VAPOR
AND NITROUS OXIDE
by
Darrell E. Burch. Edgar B. Singleton
Wi.bur L. Framne. and Dusleov William.
, , , .. ,• .. ._ _ . ,, , , , , , .. .. ,• . -- . .
CONTEN'Is-PAjRT C
Symol* anti hita 2
II RATMV MMUMI 4;ZL1TI 3
Inrimnatal Phalts for Vi ftO banU atVA6L 21,61, 15,1167, 629 Vni 569 arl
Bud Intmulues 38.40kni. at 5532, 370D, and 195" CN 39
ammii4
AWmN I A U 3K PR A P?#CMUM.
List of Whies
smsavisaf O"Mos" 1
SS4 Vw.I.bm1a &WAtS f VM ld NSOM i
m~ioa t f us a* uw " al *a6 lu fo wt"I rts 1 zw I IiS4 N&
List of TaIP3l~ (Cant' d)- PART C17b1. NO. r
7 1D*.a for thm 5R19Y *ad b91- ' Ip0 BarA:& 3
8 %10Di ft ntewitltep 36
9 Datafor tkw5332 CC'-ý, Boand
10 Va' for the. 3700 *-l %D2 S3A 5
11 Date fbw the 15 m1 eelvp m 58
Lis'. of TFiW~as
1 1%* ,,1f-t-roed.nIf eiIf-1clnt I for noM h~eel 54~ bwA~ 6
a ~ m-~r.~am~uooemtelftt I fur anu 3mA
so sslt-btO8miNa @tLmolnt a for *9 330
ab owWMAI .e'uh.m .nf~t ar 0% ft
Tottl obwprtlan re. tow1 pmewe* for3.3rtCC aMW 15I
Aberoula VA'. for thu am) W, aM I~
% a %Oft! &haarUaM Ot U.A V3 4e,~ NpUNv-I- F', adj 31
8 2we 10"I abmpsuaao at 1 "b eel~ 12Q %WI'n j, cz *
" "a1% ftZj sameyti or Ve 330 ta4*~10 D w"oil 00
11 sota &beorpttW or whu 3O Gel %pu 29I
Listof Fgiwe (Cotd)-ART
Limsts of Fiue (otd)PR
12 MWe total aborptloc of the 58,0 ft-1 V~ bud~
16 2Mc total &a~irptuou of tw " 1167 c 4 0 bas&.'.rnsI v 37
1V Ama totalv aumcptla of rw of. 59 533 20 W
UNTh total GbDOrptUcm of uQ 589a IgI ft bandI
E20W. 37 4 0
16 M= Utal eauaptim z tu sar %p t1 w~ ~0
23 falsv sbampuma oFAW o. %m3 rnI
U ~ I slomat~ "m ofU mue. I** or 3Atam
Vv~
Ir 3 wf st vwm Oak rp"Ib o*e of a",'.-
ABSORPTION BY VW ATER VAPOR-AND NITROUS OXIDME
1. IN"M100=310N
This to the thirl wa final rep~wt dea1ing with the rMACLt f vwesich progran c~omer~a viU~ the absorpl.ion of 1idorared railatl~u.
C7 various a-4nopherfc Ipses. fte :cntent* of the three reports areas foiioa":
~ 1~:Ahaorptlon b~r aitrous oxida In tbe2224 es- 1 region; absnorption by carbon inaxid*in tUs region of its fundggtal (2143 awl) bandand Its first overtmeO M ( s'o Waithe; abs~~tion of nathwe beads at 3MO =-I, 1530
sMd 1306 csINO A~ Absorptionby eaibon 41osiie an aest.
2350=-IIt " ewl.at 3710; 00- 1, at ýlcw&
FINAL TW (hb~ith) i A *Udy of the relativepressure %'bwseindaeillIuaso or a11 of tbe eb-sorbles paw. GVAIod ia the reaent rea oim, awkof e~mas lnaetive 041-. 1 *- pUon b7 Nab"
we at i09 M4.1
tA pt. o bWe elet& Qa thea r"1e tresat"IsS~e abiita at
%tmt.a. tau "akd. isaros reprt "U" iebe .we" 2tolia La hme 4leawri~eas.
%e preamt rawres wvprn ts a GO~iNUMSed or ef ariesowie, Isoto etbt 4"Wr~vt, La 190 %1soma got "wart,am $a 1P5) 1w mova, Wb"11 Sm w~m ovUn ("ranefer retferre toI
soe eupeIngewa sees"ase is am0 asmquag, is, .beft AhUw. .1..uv,,u owve. ein in Ifamsue s am eeweam ue 600 a& USawr 1 SMd Vii lot be 1rep~ed, with goe smepUne C UIhnth"
at samila$ lour vq, %eble to desasrIhe he). to Issue* IT.
arge ec"SieL 01" ns.iams" a esui or W~o qw~ am~ep*m to low%f000 "-I regiona borer. We pwaa e o w sa s mg postpmed "A WIL wilrbebly be mese as a pane of aosena !'naWe pnpw"Ia0s Wa laha! 14A
Ya!.3eaw of absorber partial proamnr p, total prsman. P, t-n.9Viwolont pmessur Pe (defined~ by .qoat.1j (5) are expressed !eaunita of I;absolute. Ahuorber path 1-np1~b. ame tob -a Wdt,.aof abgmrbr e~etati-m w of vater repor are In w-Lt of paec..Vl-table comtinsutm (hbhrowlitad pr. cm) W3ich "rereents the spthIn oentimters of the water that womaIA be obtaine It all. the vater%iow In a oobi eactalning the boom vane comfammd out. So mous'.aof @boster eeaes~awtlon or other pa" esles wre upromae, In Sultoof atm.m em, and are to-A by rnltiptVng the shasmewo path length Incm time the abasabar partial. proommt in auffmpbawea ecermated toStandrd tempraurez.
lreqweneiea ad valowe of total obeogpt~cafA(v)4y, Awhe A(ifr)is I observed rmZIb1 p41..rotiou at *fretoMm v, ane In mait of
ma I ad beedtmuw cc ~k(v iv, ~wre k(v) is the &bMPItiescoaftiiet at trowasm" V, ane In units of atmos,. 4mI .?.P.
UI. AMAXIVI BlOADOM1 AELITI
A ustboi of meawir4 t~1e 's.f-bzoamiaig albilty" Of V. lktftb:' 14;pm n.3M1,e to Use *Uvoeiasa abut? of the Rce-ObsOtbn Of NI b" twoms giem, in bwwt I. It vus own tast the UaaAIPS of taoWI aC..orp-tAss data vbtMwA from euqies amtSfting 12 &lo=6 VI* 6 Sm beubldg 03man s~ipifmi b~ ume of am emhlvmftaly flteralmod astlo CJ MO bMAw-%4ng abi.3Jties ut the puma. U7.m bnoleinmg offset of beth Sam S
Sm be- lqp in tomm of* hagi. vattoble, whib Is oaua gooqpivslet pres mA aMIs iursmmi balmw s ft. (5); OM the temI ab-ssuvua "amS beeai owmm"am fesoties of two varlable:abseboar e01
mam~asi aavlu Ium I a Useie au l mtomllm Of
Lat" um its ewm Sjra. Im the mae of iafasaw ahmwsorm,daa ~a bvem~ of Oo eMafve broammINg ObtLtias of pam peen
Safmmua emeosLag Use osala~las mOmO eanum of the miLOas.*lob *we alwasme by uvaims twom at laftwooinmtiabeam 60=*
iqm~, a isa iige Us bromiagm ebiUtie of mnbooWbisawsem mto o n b s#1.Sw tw~S ofti a"
esetmsiml with W& Us voatl bffoohIM sibUlti at M .to pams mesle wUuit me ~pgm sam m ON OkaM Ui , W4 *Asksew. amoas *9eip lbumm agpm tosUs aWM of abm S mbeawrftn at *,olatm" wwe as" go" 40 ea" abb.
IM MUiulbt 0 at a i s~S~ M zU....l Unat Swopsiw-4tioma Ise In so.st.Rei fr*VAeq F of ebsbta ownm%."bimalie Sao It Me be tow "at the bau~hwwh a of a val~iafin
"MrsXJLSA m Oborof witla4. of th* 1-% "to ~v wit vo~ma,N s*amo me q"ttl emulftsm, iiaitars or the Wbembea
.1a1a u* m~a.e" %4 Ui6 3-t. %Me b La 5u~tamm'l eeMIM,2to as S hoas" tup e *a Is a* aw- of th bemis miMu" maaistSol N ,s ah~.m ata mulas ur Us-th y.
~~inme ~ "G~M a 4amjs"S thet a.sommawsW"uritmt san fatla ft apuea uim, 5te
un t %b Sw paDu easm&%" is us alwarlbui "nt - mAM~ Sis amialrae to eambom
ass
special case of a binary mixture of an absorbia. F'~ a aad abroadiening @Rd b. 'Me sinmtion in (.ij will in %his c&an have LWotorus: a eelf-Sroadening term 'In vhibi I - a, and a second term tc~rthe effects of broadtn1tj& by th3 inert Ve I a b. Eq'aaticn (1) UI&L&ames the form,
a 1 [_,VX ] 1/2 {a(Da"a)2 [j/2 + W 1D,) [±3/2 ~2
By reuaLWin tht the partial pressure p, o gats of th* i-thtype is given Toy p, - N~kT and by assuming that collision diamtersare Indepefdent of temperature and pressure, one can write (2) Inthe form.
v'~ro Ca,a and Cae b O es~tant involving the optical COllisiondlemotere sad woss of the ebsoabing and bromimnieg aeas. Sinea
is ~ ~ ~ ~ ~ ~ zyeso form ofPW b0e z 3 nU
k?- Cs5 b ({+(D-1)IN)* (h)
lbr *a C /C IsaLL4 the seit-UroawaeIng eoffeft o)at of theabobigjh QONrset the ratio of the s1fb'aat.
ab,111V of the eaborbl a" to the nwoateUla OIJ.Ity, or tuesoesbearblmg pa. bathod for 4otermlsing I t,)r vwwm a-ioufs e4agaowe relative to %p wIli be 4escribed below. te am Is beaseatois (4) to valled Usa mmsa1-s Poe~ of th" pa eaqe.
F, * ON-IP 0 D # 2
"aep to the partWa paaasure o Mw te bsorthlv S. am P Is theuewras 4 s.wal pressur Ot Lk~ eaqe mL %A tme abeesb"W~ VA and
I 5 tht toeo UP r Aisess F io the case of p OV.
us~ -,-~.-~ ~.?~a ivntzyperatzro a 'rr V. etto P.. MA oine the wvaft o P be. bee" 4eterwASA It ts Poeetbsto fteecrbe the 'Vtsag efftot of moo pegeso As No ot -
* C'.~~ .t~e It am___ abaft L . I %bat the free U o..ebesorptlos. (.) -J Vwth a b l Osorpt 8, hV)4V we Iumutweat of axy~wn partwtors, Fe aid obesther noeeu1,rattoa v.
She soperatmetl detersdobtlas or a Imeelvo. a $AM )f I"etsaau"Ifae t Of ate 11144,U0 cela M SOf "rtiterat 0%.h IS 1610bWh abeoaber oommneetritoa w to the saw. ib.1wqi isgs, tac abrtseau, g*J1iq4 the teeoe ,, easlta 0! a POO mL* 0"0 t khe
'#34
ebsorbing ps at presaLwc p; fcr this ý%e! pe. repf. ,,d thpeqaivalent pressure is given by
Pa - Bpref (Reference ceii). (6)
The "cq*e in the loner -ell. called the "sample cell," tnitiallyconsists of a saIple of the purp absertcr at the partial pressure .required to produc an absorber concentration w equal to that in thereference cell. nitially, the absorption of radiatlon in theIs.ic cell is ccum5il.Lably lead than that in the reference cell,since the partial pressure and total pressure src less than thosein the shorter reference eall. Various amounts of 12 are hen addedto the reference cell corresponding to equivalent pressures
ee N2 (S+ample Cell), (7)
where SO Is the partial pressure of the broadening Vs. For theILiaLIoN in whica th esooptlIons In the sapple end reference sells
we most nearly equal, It !s assu that the values mf P In (6)am (7) are equal. Te value of the "If-broadening coeflicieatcan then be aetermined from the relation
toer i the parur.Al presewm ui % iii lw I omple cellwhen the ceoerptils is Ume tvo %:*Uks are equal It the reteoreeecell "ae contais •i at a partia, prosesre it ce* *sal be
wclue of 8 mes etermimed for ectorel of the aseomrtfeSPAlN&"4 is TA preeest reaer•b proem Sly aaing Nos of the
toub1e-emw r-,-. of tac Perats-awI r Mom, al opeceumstwr. Iasm a*ee"* a fi.i .€ e b-cr oe celU ma see w e tohe Uft-MWIV eewith a 1.55-ca cell In the ,cIlomeo %emi is% other aes** a mWimnforem.e eUell w soee wi elther e f.oem or 16W-P% *..mle esellto lawealipte oamples bawil" "mI "amev ofV
ry~ictl opeetraL aampaiece Walch wone Ota4m4 to this woror the 20h eWI %0•ud a"e*Wm to Part I of •g. I or virie
values of %to*-l pressuer Is the sm"Le coll. tho apcetmostwren--frde44 kh,- rit.tn ^C t)W trftme"CMoe of thleAM*)* cell te••. ) Wth tnkd•Wseeol a.f %* e ntrewtme •ell ret.1 : the O d lire at
M7'
T1a. 04-______1693
- !.Qt~J/h/~ 179Iref. 1i'-" , 84
0.96 "' 2?
1.4I
z\W01 48
WO..IL " 20m-m Hg0 tr 2n- to
U- 40run.~ ALONE
23OO 2200 2i00
WAVENUMBER in cm'1
%MM preem"' to r'ftwou. *aUaft. - e grm. isA sa me raI. fur as" otami
Isauffi.not o v a 1*suta crat r*akt4a U atww
a"o .er"m sho &IS for% I asgua tthe ta"V! Seams~a biwlt~ Alfalat val~s of S
1H I AW %Wtlu~s 6bWPtl OM11 Is AGN La 61W aM.
Tsa". )/T(ref.) - 1.00 represents the recorder pen povitlr.n when thetwc, 1beens vere "b&lanced,' i.e., the transmissions or .uu;L ,wýitswere 'c earn. It is seen that the ratio of the tra*nstirions -A*-
crossed with increasing premsure in the saele ceUl as would be ox-pected, end that soe of the eurves r*prese"ting the ratios occar-oev the balance line for oe frequencies wnd below the line forothers Therefore, the totJ pressure corresponding to balance usnot the "me for all frequencies; the prtaxur. eo-reompon•ig tobalance for any given frequency was determlond by interpolAttng be-tween the two successive curves which oet-=.r on oiosite sides of thebalance line.
since the value or P% corresponding to equaL tranmmission ofthe -ells was faond to wrv with frequency, It it appareat that the6-oiuoe of D TvhLri ULroughout the bwan. PuLnaLs urmes;-ning to theexperimentally determined value 3 were plotte saginst freqenyIn Part 11 of Fig. 1. lbs collision cross esetion ratio whih tissbov b'y the rigbt-bend seale In Part 1 of Fig. 1 can be shown byuse or k~), ( 4), W.~ ( '46~~. rilat.. L.. Z b
I jft...I1/2 [_%Al (10)
Where Me I the ame- of 1te 16 molecule 04.,.
A' typical eheUW7%On eurve of an IIQ0 seV to IsW~ t.ov Psart IIIof Pig. 1 o: r PAer that e "•steturee of th ebsOeeteun cuw casbe wrz..la.K. wAh Lbe struackre of e curre relauag Ia to vWSwWor.
In Figures 3, 5, end 4 a re ehowth curve& of a ws. laveUMhlbeand the related eul. tse croso section rattio, for the )M em'
1306 cS 4 Ck bea Nae for We to me 61 me" roogm, v•e etivelya typicel • beoeyt1:- ctres to at Is erlz ttpwre far eOafriA01e.Tae ZIAvee Qt B for these basis were CLi. me. a.Oaue ecethe valito of I cbm e very 4t*lattely t1*w Aout th, %amds. IMvalue of 6 we found wu W soen maeeI4 ceeet5 for other beaftiwaoettptV by the lt* described above.
it shoat" be u1"d meat Lbs cestway or Q0e Val" Of adoeto•me by this ntlw depolkpends e4t oo.,s s eeu ea-y to Wiebthe obearber t- v to mode %be o e toboth the refameeand saew esle. TZv wea o met tMe o a tbe" L aes, * Nane evilat I would be delorma41 the ~he of the eyrv relattegS I toaemmbr WOWAg also be if e
ls of presses of 1•tmrlg 3 for 0t b bum, fs eof WLsehewleg litfrresti 1vlabe *I v &W F wveT' SM4; GUlSe of 1!wore .e$W Pp~rwly~I to dat@61vo 3 at freqmweeei of . ~4 V eu beesytiemI11. ummles Ifi anpr v. wore 'ssI I Is, Iseset ftl thbe winm or
B 1~L- ' DCH4,,CH 4
1.2t I 1. 0 4DCH4,N?
z 00I w=1.35
atmos cmo20-
m PARTIAL< TOTAL PRESSURE-I- 'PRESSURE CH
W 4 m 760 2.8 mm Hg-
CL 3200 3000 .7800
WAVEFNUMBER in cm-'
116.8 A_ We 5e" ftla I* or"f
B LL.LSLLji7I0.
zo 20-PARTIAL
0 ~ PRESSUR(/)40 H4
on w=1.35 2.8rn~mHq 1< -otmos -cm TOTAL
S60- PRESSURE-O ~275 mm Hg
z
1404) 40 1 0
WAVEINýJIM8ER in cr&*U& vo- ý . r4 ý ý fwwtt1.Iint b ew "aXV ,C "
rl fa 1"s.~ twp%&m w e*@ *us m fre )L.
1.4[ - 1.25
DB *CO'
1.3~ Dc 0. -4
09m05 cm
660) PARTIALz RESSURE TOTALý
cO0 PRESSURE14 1-24 mm H9 15Orm Hqg
700 600
A f 1bIel obo f*J twowe ath to~. & fur ewcw lt
the ba~nds. The sa,ýp-s wc.e formed so that the f~ractional sarnorpti~oof' the samp~les being coqmredvas usually boxveeni 0.'1 and 0.9 In thespectraJ. inv.-erval being investigatea. toir snal.Uer ;raczioflah. absorb-tizoi the spect:-ometer was less sensitive to small changes in prewsure,and thus, the total preausb..! eur. Et~ponding tc- equal asoarpU.-jn in Q,,two cells coule- not be determined as accurately. 1Por values of frac~tional.absorption greater than appxvximately 0.9, thec povex- generate±n ity 6Ldetec'tor was too loy to 2roperly drive the servomechanism which co:.'niosthe comb in ý:ie rtference beam; a false r.-ading might %,he. be obtainedunless extra care wino takonu. This difficutty could be overcome to someeytent by Ir reaseln the aniplifllr gain end 'n,ýreeeisng *"! So.'ennng t-ime;however, as the fractiunal absorption approaches unity, Use el'fect. orscattered light of frequencies other than that being studied might becomeiipo;tatit. and give rise to false readings. If the scattered light wereeqiually inLentse in both the reference and the sample beans it vw'-uldhave no effecL on the re-kding of the apectrometer, but it is possiblethat the Int~eniiities of theý s-ýatterred light in the tw... beDAa were no,equel; and values ýf B were not calculated for samples at frequencies altwhich the fractional absurptiu~a was greater than approximately 0.9.
Tctc-' prcazsv were L.mo restricted to valusa, l.i L!,r. approxi-ma~ly 1=0 am 11g, since for larger pressures the spectral. lincs become&meared and the dependen~ce of absorption on prescure beo.-inea lefus.
For the ranges or pressures and tractional absorption of ttesamples investigated, no dependence of the measured v."ue .'f B at agiven f-!quency on eitheýr of these parameters was Zound.
&4Im of' the latu ware *,t.tei'u ti use or' a iingle'headl Perkin-lner Itudel 99 spoetsrometer wriirh vat.* ea~cnted in a vacuum t"an't. Thisspectrometer was used to determine B for th- 1426U cm-1 CO band, sinethis band could tint, Le studLied by use f the Moeld 21, which was!!mited to fre'Iuen':ies beltiw ~4000 tat c .. ~.:: the prism uimed. TheModel 91 wac alst. used to invettigate tho total absorption and to mea-sgare B for some Ptr'1'g. C:.& an-d %0d homIAe
C.
Since Lihe Mutial 99 iii n, :;nglz-beam inwLnmenrt, IiL w-.. ..ot.to couipart .Am.Ltanoously f.)e O':act~iona~L a.z us ." au4,.s. .Lnditfercnt -r"tt tby the method dpwzriiod ',n conne.-!con vith Fig. 21.Instead. ''rsof strovt]." cr total] obso-Pti~o wer-e obtalned for varicussamples We,. t' or more lifferent. "l. ler.gths. The "effective" vallue
'ý f'ýr the tntire bend P.. . the .o )ves fiv i thop reý,sure rat'2r-r- for a sample- ina the longer "P11 t'ý ,riM',po the
absorber coacentratrin' A Atmuple :-ilculatloa for this method of doteor-mining B wets S!v#-n ina Report 1 ina cvnneetlon with the 14260 cn'l CO band.
~'"Z.aj.paralus ib des:r'rii;.i in some Let~ili in Appebndix T c'l +1,e
263
The present research program dPPnls primarily with total absorptionisl~her than virh rractio~wl absc.-9tion at certaAin frequenniee. It Veitherefore desirable to obtain a nominal value of B which could be twuedfor an entire bend. The method ýf determing B by use of the sainlk*beam instrument, of course, yjij such an effective value of B since i".was aeteruintd, on the basis of total absorption. In the case of bam~sat~itded with the double-bean spectrometer, a nominal value of B for~the entire bard was determined by taking a "weighted average" value ofB from curves such as those Ini 71g. 1-4, with extra vet.ht given tothe frsquency ranges which contribui~a =.-t cf the absorption.
The values of B determined for each bend includee In Reports1 end 2, ms well as in this report, are listed In Table 1, and whereverpossible they area compared to the results of other workers. tecept forthe came of 120, the tabulated values are believed to be &,!curate to
Sas en effective value ror the entire bonds.
It Is somewhat more difficult to determine ki for BeO b~r.e Lhanfor the other bend* fnr two reasons: (1) the value of absorberconcentration w of an N.O sample cannot be fotind as wccurately becausaeof the adsorptTon of ts N20 on the wells of tea absorption cell. Themethod of detrainng for 1e2 samples, which involveu finding the dewpoint, its discussed bolow in ie ction IV; (2) te range of available
partial pressures of th is limited to values 1.io than the vaporpressure.
In the Investigation of 0~, a multiple-traversal cell whosepath length could be sd-.uctedNy eCxterAi controle, war ueL; doffart. t
path lengths corresponding to 4, 18, Va, and 32 traversalm were there-fore easily obtained. Feht curves of .rovth of total absorption fordifferent samples invostifgat• at lifferent path lentuis in was posrible
to deter-mine B Csr the kriQ baendt. Because or the limitations ,tatedabove with ragreod to the ccizracy of determining 3 for the H2 0 b onds,the value may be in error by as much a. 25 to Vt%.
It is i;p;vsat from the curves of Figs. 1-4 that a nominal -tlunw.6&A. Aj41 h - 4 .! uita toi~alt a~eboi;tIon, 16ince for
fo-p total abeorptband th mAjor portionn of the rowth occurr at.dtlt'ereat feAOibthan for sms.LL toA.a± absorption. Since the anomun.V"4.A;: %,f vvj~signd '11 eWaidi~ug" toM V11jUu or B at 4i~L*I reqAencimbaccoricng tr) the contribution to the growth) the best effect voe valuefor the eotirt band would therforo change sith total absorption. Bow.ever, tý is mcvw fr-a the curves of Pigs. 1i-4 that B varies by only altho pcrctn t for the ditftrtcý f"que*-:ies, v nd any change in the nominalvalue o.t, B $.Ur the entire band would be negligibleb.
Vi was stated above that the asured value or B at - V frequencydid not apparently change with pressure or . fractio. aboorpt±-n4,. 1I'Ift. ocv.! vhie.h thd. .&rehx tere wn varied. o V-p.", .eeA
Ni"''trhe , in ar oeib e rn e n ror b' by 2 OIn t2" 20 . 4 -rn region,
I•Iss~eva •oeth uresof71e 1• t 264a •u
r4 rqý4 H 4 .4 of-
40
.4
.4 rq 1
CW4, I-
84 'W
265
have suggested that the value of B shlouild inereani vith frartioralabsorption. This phenomeonon arises from the f't. that the apectrel lines
-In' not havYe a tru.e Iorcrtzian ar~.1 tniut a.1r 'ar.more in the wings than does a fureign-br•adened line o" the & half-width. Since the lini! centers tre virtuallv opaque in the case o.. 1:52ezractional absorption, the only grovth with increasing pressure ru.it"from the wings of the lirws, vh.-re the el.'-LroOadened lines are strongerand the e'factivP- value of B Is increased. It was not possible to observeany in~crease in B with increasing total absorption in the presentir.veetiption o: H20, possibly because of the imaited 'zaluesnf V and pwhich were obtained. Although, accordirg to Benedictand PalmrlU, t~evalue of A~ Rt a given frequency in an 1i20 band night very from approxi-mately 6 for small fractional absorption to 12 for 1are., fractionalabsorption, one might expect that the effecti.e. ralub for .a.mi..ing totalxh.,,-tion ci as. entire band rtight not dievlate appre:±abi" from 6 sincet_' a.l.or Portion of the growth or' the band occurs at frequ~nciecf- rwhich the fractional absorption Is not large. This result, kitch Isbased on theoretical calculations involving the shape& of Individuallines, has been contii3.;J, Ly Benedict,). to a large extent by ,:Alation;based on the result ! lf total aborption measurements .f H-f era., r*-portLt by 10W. D en•edlct found that the HN data yeildedt a value of bequal to approximattly 5 the same as the value detsrlimned in the presentinvestigation. It i noeted that COW ued a 'Tveipgoa" pressure (P]]p)for the 920 bands; this corresponds to B?, a va@je which l1 believedto be too low in view ur Lhe more recent experi.ents and theoreticalCalculati ons.
Value* of self-broadening coefficientt. for individual 40 linestmvv Lea;, lutcvrained by two difrerert sets of wturkerq u-irs litterentmethods. Vasilovsky and Neporantll, by considering the total absorptionof a single line, found the broadeni'.g aoility of B20 relative to thatof K2 to be such as to corro.o-Vd to B-6. Iaattl
2 found the wmsured
balf-ulI•Lh u" ruur s^lf-brouiened nhl) lines in the )XJ-txW cm-1
regionto be approximately .6b - -.Y, times the ealcuklated ha)•f-vdtb of of 'broadaned lines, *tis result corresponds to s value :" B vary~ng 3verapproximately the sum ranwc, 3 5.5. i
7Tie avjoaiv bwuadquijag abailix-ies oz vw inert gu~es @oanob roundby e zlijg th% rartial pressures of each jas which is required topro&&oe the smae tow%. ataorption when added to equal tv"Wleb of am. ab-sorbir.s. The method used tn the present xinvos atioa con best bodoacAIb.i by rt'eorning to Fig. 5. A sample o? ý;. LaYing a partialipressure of 104 = USg vas p.a-ftuced into a 6.35 am cell, end the totalabew-pteon of he 91s c0 aCO d mae ,w.eauared. Tihe eauureA walue oft.,.; absvrpatcn was plotted at the loer end of the curves 1 TU. 5.fte of th, P ••4i guses, Me, f•or edplu, was then added t the cell tototal prissurae of apWecximately il00, 400. 760, lISW, 2200, and tVMf vo WE;ike tOtaLI Ai rp! L•• r• t .u' meusred at ach, pressure and the rasulta formedtt- Dotints v.iu; -ne ctuve or Fi 5.
266
-, .-
Z�.Z - - -
*.DZJ -
- �
- LL-- - -�
- a -
-� - -
-a
- V -
ha -,
-�'- -
- -
a� w� ?�.
ThLz Ptuce4ure vrn Use, rm aated ror aaeh of the orhor hktmnlen14jan;mare @us v aIw'ys takaL tj start vith, as nearly as possi~ble, theame Sat of CC fro each set of snamples. Ih* total abaerptiou -%f xcicaUPle Of 00 &Lone van imea'red before edallag the brtuadmaai &ar; tLeaarnirnma7 of dble value of total abSo ptagn Provided som indloatia.lor hw Ruawly equal mere the values of absorber concentration for eachaet of samples.
Fres the oumye of Y111. i. ý.t can be seen Mhat a total Preasues of960 am I*s cLa xehed o rduce % rotal abeorprAmc of pO Gw1 wItA kwaed "c '40- broaemIang gail. a total pressrne of 1450 - HS is zequiredto uaedza th mm total aboorptioa with Me used an toe broaieming &sa.ilac 0 pItUIa preeamre of CO is ).JO =n ig In oth ceaca, it L~s ujin-eluded tht 1550 - Ag of Nas anrewq~uired to produce the saw broadening
A qmntit3 &a.Ll"d thu fore&Lm-broamag coefficiewt 7 of an imortpan 1 va defined by
vb p Im tw jatLe~) precaure of gSa b required to predmac Usememline baeeMdSLug 0a & PIWtUAl Pre 'cure p oft3. TWOr, ftm use *xmmleebfte, the toteigs-brmimivg emfttla"O (3 Na ia 860/1350 - 0.64.Vala.. ethaime @stae, all "eLosat orfi
Yalme of 7 vane dtm lead in a stmV or' wwwn for the OtherbreedemLa gume Imehuje in 71i. 3. alcdantina veo. inia at ammlaliffereat maums of %QW a~apsm."o to each ga; mat it WA PB %thUIthere We allflMaa iapS&.na Of 7 UPON the ttal aewpAincme, *1mb.of emia imarem"e with tota Pressure. 0", there tote eonmlWarthAt ma mamboas va1w of F "am be tomm tor OaUR Urcm~if 6 pa ta at-%s abemptimt bamd. P.d that ies mius ha b at Moat a aligt 6ffpma-on" ma total abeorpi ion or preaCre fnw th romps at preesme ilmlWu1, thu peemat eumd~..
"'Asai, the W' a 1 COg, tb0 Or' 024,6 Smi t 0A .-...
varIous "wt pee.. 2 reoulta of Vae mawamata we hitAd LaShble It. *ielj alao inoludee %Me plal pecwre of the aheowbifg peeAM the rampe of ttal proswqe ~m *hih ealoulatinm or r we am*.*3cc in~Aeod 3m Able * ar valuaes of~ b/Y hIleb an to eýtie. 14. (1), Me M lahe rmc val A-.U t U velfA~ %0 P, Usfore-breeedmaiag ooorftlelnt of pe b, by
v~tor 2 to Ids thlet~ular weight of Ng.
268
Table 2. Fureip.-Boadening (lo4felencs and mRelsatiw, bbltcular Cross Bectioam
Phuarle-Pressure Total .
Absorber of Proius~rt Da bam Aimrber* MnP BrosmjeL*r fi;'' 3'
3and (w!~ (mg)o (m
320 10 25- ii. 0.73 0.582224 ca-1 IOWo D2C.85 u~j
A 0.78 r,91.23 0.641.08 0.9..
100 I 180- Re 0.70 0.574M5.- lout) 321.21 0.64
A 0.83 0 A
021.17 1.14OD 0.97 0.99
;ehl' cam4 3k= A 0.78 0.9Be 0.65 (#. %CUIA 1.19 O.96
Co50 80- 1 ~ Oiq 0.5223 mI70C 0.6) 0.9
0. . 1T OARA 0.76t 0.93
1m1 1)00 ou.5 0.56
1.1"
soon 1.41 35.an
?mOw.1tati valuess 2?F pma bout.n4 &awoas4 to less tMA to.
269
Uwe both the sael-broadeinmig acoffi.-iata D and tkis tweo1a-brca4anuna oceffl.oionTA F wre baedM on the broadenin.g ability of %,I+f*UQWv U~t Z%. (5) ceu1d be SMUSULew 170, a .emrIti~ contoiLiUg OTelInert bradoolmag gnu.. bj to yI*M
ILare Pe IS the .'puye~alt woesur, p is the WtrU'1 press=*o of Vieobeoiruta pas and 71 In thu e 10O-btoowuimnI vooffteloat of tke I-th
UNo of Me pnsoost results an the amseaurvowa oz oelialso erea"sotont cmxma*oooa be compared wIth Us epwautm of pre~t-9' mrtlpCossawk Osslels dotarsased ,eluoa of Us ratios for. arAw f. she &mom
J,&ozt Sam" as vers used in the p.aaezt :=4 by obaarvia the freatlomaae tsaat a glvom rrequaaoy in the 3143m oe CO eMdw the =4
c-I . bum. SUi vtbod Is In aom~sst to the .'tis of mrnalttotl abeeriptla vhieb 4" se iaM n the pIamset sak'. Teresuls ofCrssa aM Dnaolsan o aqwvd with the paoaat oGait In 2bWO 3
labie 3. Comprison, of #^Us* or Con~laim 4weDog tieas With Rag ita of Cross LLA bd
b 22 ni-1 kM 0011 I wCross am Preo*" % Cross eM ftroseeA,
ka 0.70 (0.0% 6.1 0.66 0.ýo 11.5
A 0.90 0.93 5.6 09
C,0 .0
Benieseb and IlderI4 used a higb-resclutlon spectrometer to observea qxmaatityv 'roportional to the line width of an individual rotation1inM. Th resUlts of these worker., vhlch were based on the J a k -P2.nse of the 3020 ca-l C~jh a--- cuaWtd aim rar ea s !aapplceble irTable 4 with tba preget results based on the to~ta absorptio fl ? thiseam C1 buAn.
Wta~l 4. Dmqrlc-- of BrtoaiauiIng AbIlit'las am.Cu,115.., Cross S. IOGA with Rasd"Le aDeneach and Zlitsrl
Dreuismiug AbilIVO' Collision Cre s-ettons"
lecmaeb end ?"*@at lemeeh WAd Frementb Mier t 44WAer td
1.OD 1.00 2.00 aaA 1.39 1. t 3.0 .3
1. i I(i
CO 1.73 5u
0 1701.91 3,7
kObvaeeIng biityv Of la norusuaed q^ LOUu.66C.Ltisione ross section norft~lw to %,a 0.O
271
MAborption dAA were obtained for the 2563, 244L, 1965, i11e7, QI2an 539J mrl "- hands, by =a. of a Park1a-Mma 116-*1 2 4mahla-ý[email protected]; W&a MCI prima Interchange unit mw ULaa4 fzt aUl bl thelatter two beoah, for which a Or ut, wase used. As ine ptawwiA.x' mvorts"ba data an prsented in tabular tarm and by 'shoing rapreentative Sb-
surp*tiom mruse; aid the observe al umes of total eboorptt, we relatedto Uk* " herem letr, absorber AturstFo V SA eyawehT"U pessem
Iby the wa of curves. V1iw. -Af sqavlmlat pressure vow calclaefor *cc! sump. b; t-be Tfalwing egmtlem:
W~dZ V .16 VM WI&IS WO5MM O to I&9 at PltlJ P.UWS p VUk* No Ift the OWaL1S.
Im Fig. b an 66aw .QpeI tative abstaV~am, curves of the 2%63sa 2"1l -C.L beside tbe vales f smid Fe amS5PlMA to mo OurveWe5 In.1@tAt. Mhe eb*sirVUi 4910:fer tý&* %M bMsA We .116 I&
In she 1eftband Paties of YU. 7 %M Wl at bsoarg CI the256 46-1 bM Wa et platted eplitI 1p With esaft a awzsernjft
to a Comm~ met. vak of. bhe W&W.l. Lee,** of werve eed~Ar totbm. Pe".M" I Va s Aus "we e"aumm Im, **"h~i.Low 4ULU ishewt I MA 111 eat be ew. mus of %*%Il doerpui vaeUm
mlaewM umm a* emu a * eve I& u rl&*t1-N pmm et Pig. Th" e usdto Vf"W ted et Us tl. abuerques e a k--f ka mmo Is
easept far VaLuse at "%"i sbebnrpusU s ins. mews mly 30 40Val Q aver is "e~. t graw
A ojaLa~ set -i oserves won dx for Us Aki ar %4b"t"14. 8.
&ususasserespuim Ourves,0 gt &; ems &&it so o' mare .ODO IsFi. 9; eMA0 Asm fur tap" I" twad am tIaumiU
-~ .- -.. .u of W;Oe ujAV"f abm..iapra 15m of %be I&%,me 330al iss no~ese I . 10 ad11I U t nsm so we
*AL or %1* 9%)~ M1 we" pruesseM Ima ft. 7. 20 resu lts fo 0as-' %a bond an %Iac at-m in nog i.t "a I%
~ ..... * ~ kavi mumM±S& htoul ebewv3Iuom at 04. em mUp es-,dSwbLa aI. ,~s Ms., WIZ Z, . .~..4 t. VI Peeve
study. It is n~th"y atmoult to sow., S~e ManI±C: -ý %beem u- -. .1.1 . t au. U~.0 i Ift"25 Shell s I " -% tiat, . "A lu"
v*WWV P I. a¶ '1) 0.4 U. *or* proam"I. to. MIjA% * oft
w=0.38 mMH
~ 3oV~~ I 206~N______0 __
7 4 6 i~0;
r_22.4 I.0 42.4 atmo
U) 20 10 cm
742
z60
ELi
r01 \'U N20
c I.IM 24%^t~
WAVENUMBER in cm-1
14 .Aserpsum anysw tar = w-I am t~.. u ape mUO"re" mtlUs a t o~~awuw so ' ft nwmge at ~Authobam var "v~t~od.. SW m &it width agals SWOOMsi
273
-aold 5. Dmata trmr the 2563 AMd24i61 coII.0 BwiL-Ab*
p P e v JA(ir)iv In alatw's 2r,6, a-- &.1
30 Ng m~g %:mB Und DaM
10 jko Thl 0.075 3.2 0.do2 -I 05 5. 2.)B3 40 00 206 0.38 q91 3.22
0 W ~ 7)4( 0.36 13.i ;'. 03
6 iou 40 "a 0-'r5 16.7 .7 lou 1,40 752 0.75 19.1 6.08 W~A 224' 1.5 n1.86.A9 am fl 76k. 3.5 31.6 X2. 0
1. Itj 25.k 2641 N.9 21 6 1.
!= L-W -7ýe m
0- @0 * 4
16 30 rkhý ?a.. 18.6 OCT W7
%a 116 46.4 106. )
-'6.
L66 1) ~ 6.-, 6.6 z-
-'4 fr. . L NO4. V-.' -7.0W4 P &
o274
!i• .. . . !•rT-r-,- T-.
'!i'ii'
ai\ \ " X \'I 1r •a..IV oL•'-\ _ i0
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!-, �r 7 r -
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U0
£ N -, EU
* - aE
- I;-t K
- bI�- �
.- � -�
- - -4,0-� I�.EC -1
- 0�
'*, V 5
ET* * I
� � � **:�* 12
23\ \ \ \ 'N XI' *� ' a -
� \� � � -� * �*Js
I, -C* � C..
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*� \���13 *�9
-� ,�. e; o a -�
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0L20F r7
40Oros cmP~rmm Hg
60k- 3.21 30.0 -I j 74
0a) 07
(> P. in 7-4ý
D 2L Mmn Hg atr-I - 'b c
1 10 11C 40 1 I k
L6 1 7400 N2O
WAVENUMBER in cm"
Fi.~.AbU'Aption mawm for thie 1285 =-I Md~ U6.1 a I *Pe
4t *Aob t~b* bainds werc 4ivldj. S1*etteI slit wid~ *lt. 1£w.-Jabtely 10 ca'k,
TRV±! 6. Daots fcr 'li if)A' andijjf7 cIL- 4 JI2 Fiands
v (vdv In c-
Pa1 P P atfmoa 12t: ~ bmm g Nj EI t~U CS m
I. lou 1%1 112 0.75 56.4 5.41 00 2w0 W~ 0.75 46.o 6.
3 lr 4m00 1 0.75 ý5.5 7.24 10 740 752 0.75 &1.4 8.2
5 100 I-su 752 0.75 60. 5.3.6 100 1475 1485 0.75 64.2 8.07 1.00 2290 2300 0.?5 L65.4 0.ua 1110 3050 V0W 0.75 66.8 S;9 100 100 IW 0.75 16.,t 5io 100 7a Mo o.T5 60.3 7.61i 100 1470 1480 0.75 61.7 7.7
12 10L. 2290 2IS0 0.75 6,.o .13 100 >.)'0 ioo 0." ? 8.2
simirtfiia 460 em
Il 2.9 2.9 * I ~ i.
15 2.9 10.) ii.2 Iy av17 2.9 2). T 1.0 o 37 )0.1d
19 ;t.9 232 237 1. ", 51,ý20 2.9 i56 -t50. 1..P 71.4 .a.21 2.9 `10Y 3035 L.5 76.0 2
23 S.6 12.1 13.d g if;i 511.b.i' . 6 5 Wa 2.4..16
t., 12.s %.Z 13.0 . '
53 12k. ý55 ly.5 5
32 12.k 196 196, ý: e i i-L2.4 7a9 7% 5.9 go,%
Iles
v SAt'A in ca-l
No.Pat mH. mt cm c'
35 Lo,.0 20.0 2u. 2 9.3 57.6 .14.8M, 1,. 0 40O.0 '.1.2 Y. 66.8 18.8
3? IC. Q 100 101 9.3 8o. ', 25.038 10.0 '.00 401 9.3 90.2 38.0
39 10.0 74'0 -,41 5.3 92.6 '.3.0100 2ý1) 2310 J.~ 6 iLR.8
hi 20.0 2-3.0 22Ah 9.3 71b.2 23.820.0 bo.0 hJ.4 9.3 fli~h 2.3.6
L. %0. * io&.0 9.3 91.0 39.020. 0 06i 9.3 % .6 5.
45 20.0 7140 71.2 9.! 9jA.6 wt
47 1. 400 1*t '.6.7 300 ýS'iQ wý 4 . IC.2 , 10! 4.
'. '1440 740 #6. T 109 T.
w Ito~ Itv .
9 he 206 211 75.6 ~111 77.6
AM A1.1 UP2 IA9 116 5h.6LO0 hm0 #&I#, 189 inU 96.'.
*To1*. ~ra .g1 .. we-* tSV1aV4 atorI.o 411.promhme-y s
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253
09orPticu Of the 1285 =71 bead to equivalent presuerae and to a 9awtityvhq1lh is. pr-lrttlolal to sb.o-ber c7cta± % ?aoa of total absorp-tion vere eqreeased In =nits of aicr~u lasteaa of cat. Ibisi jig tesI= tUe article bh Gooilr ard Vow32 had boon redoieed go seb tbax 1,: meUfftlctult to~ ree.1 values of total absorption vre cioss1y then spr4.rb.-:.taly I A. &Muwuvuj- ne V--..-' -- M *~' 4 nr Ilf t..
byp~otbetioa2. une1ee vre pruedicted by uslng the curveis of Goody andVoxmfL an by using tLe curves a.' Fig. U. fte ftret mug's containeden Absorber eameetation of 4.01 sum-an at an .qu~l~e~nt pressure ofDo Mn 1g. so auamye of Goody and VauinU were used to predic; a Sabsorption of qsprudintey 63 aw-1 ikUe va. 11 predlete 65.5 aemStai.IMly, Goody aod Vuqml~le curves ~predit a total AbsortIoN ofapynlonsnaly 29 am1 , *±Lch can, be cctpere- V-th 3 Cor V-AI-*4 %7Pig. U foraesampe of Va 4.0 andP to a = A. oemal"In a*ftat ohat Ito eurve. cninot be read very sociatelp, oe 00al~so fromthee" wwo comprisons that the Ve seat of zonalta awe Ist alee3000 fairagemat
So comes Were bzsunted by GOORY end Worsen3 to relatote total4absortion of teUW 17 7 bwA to aboaft eacn atreias Or e*iwaiinreasenre fterefore, so caftrlsoas e01)A be wa bounce thes resealto
ad those a U P jeot. saweegtoin. So mealulate w Istweaeitieetros U tiec layeetiaett'e ane eaW,"r Uelm la a mAbsestion a ohndblateoaltiee.
Zn "ag 1, A ase shr i Olde0e40tative e"~ONTUOa 241"# fto Ie 58waM -R- teafis. IM dtat ar ahs" I" les ane 3laed la
WbAG 7i only MWsapese of reauvely tam" 1 p"esed a &ADWSa.absorption in a regrion nt ** "aQ arl bem. s bewev valie oftotaL abeanpl.infa terb4~ th" t.-AVow tVLt".*t er set Plot~agatsas I or Pe wee- only a r~"~w -0 we 691nanon. *0 0-w
___mft6 b ad vao leI& at its "eAter. Ifo wrk ase total ahuwp.ttou of emb ertlca VU ~eeWft MA Liee Is *hte 7 01% wilb %WeIotal abeseptiin of ame eauitr tM.iL
A Larg path. of MW WI on 5 l a wee, Slatted a In .Iwith "%Ia abeaptis stma a a tAitio or Fe. as tr us o"W me,V61.8a VS I&A Moa ra s Cwe uVe or P.14. 1ý tr. prwrU" palate ter *aSMPOeAR %-NO. of FlU. IA. to ibieb OwWI& aboleherpUsa VW platted
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h Igh ec.uI valen' iir " ::,u r'3 an AI dw t-v i -. y; -- r --. -n ^II..
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:011. !1;6t trjn MCC~.z-'!:1 r1 ?' --- a "VeW W.10. S! pa l~t.. Incaae.1 ;'tjw VWide was Closed on. aw -T %t was SU4arved to V
W111G USIL OIalkisiCLLOG C%.L PrOUjeWfgAS~0ieA LJr4. w . 5*Inteeier 4or ire cel.- Ethar was put. into the tube auid X.) va abethrough Lit order *so 'eoo It tu:n't ci o.denasation forud ou this oGe I. ES
L;7 U ~ , wi~cih could Us c~served rtiarAAj & vzri-v In U.a *M~s~r-x;*ý toa c,911 A thermomo ete Lxacraae1 !a the other we& use-l 1- 4-ut~ml"a~ toapcraturo at. Vich Czr4cnG.UAUo r~tartes.
'ne atcu~racy vith whaich the dow pJauit tau=L le Iten'tsatte Seci;pr'mbatlly lupo how accurately one cow~i tell. when eavensatlox starl$4.and mllvo itwa hue a-urartel- Um taercoester read mte trao~
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rrvull4gz of Use Ukvvm.Lu& fale lu &.OL Mnre Uý% 9.0 b: ... t -'I 0.2 0C vhen hold at different poIUios la the Ottv-P. It was fw.6I .Aat.of t1~' rfhj-~ wac C.Ppled gIovily, a O-OpO-tt'.Je wus re:emM-C at tr:.e.n a rth~in film vou'A1 appear cn the miar~fto or %A@ tubteg; 1tif, um ovr 't
veto ~Uarvuaned, no r'rtner emandmat~a.n sees"d %o abe iWver, U~the t----;rstuare were lecrossed. by a~pproxisaiwe2y 0.2%*Z -.±e zwandmstatilacransed. In QV cage otf safpleg cof HP0 &lof*. *h W atIal weaausreci,..-1 *,= !,aur-4 with a atnamter and cowpared vit.' the .artial prmes..r
dotermiuxed hy vine uC etarzejr-s t~iai:e. rca.;f tci*.sret at. wtiche e=A-4ensot ton orcorrm! to U~e partial preassare. It was f.= Ut~a -At valuesof 3ZýO par ~L essee 4svtirunun4 by the two nt.&V ~eedt ;zomately 1 2~ percent~ If the ~eprature ued vas Otte =-4% mt-. Wae e- ezA.t~un wtkgdJ ltia'oseh', r.At!Pr Vlom tho Al".t.f.1 Ma'tupr -wMntratt Al.
a thirui film tt~.t errea.ý-k an tze rurfai:u.. g, ue L;A.J..oi
It is belie-ol that. the itkuin or v vuct, were deteminia. aceatc,"iste V, It ' or -. vr~ceat for asupl-oa v,".*e 4iow-nint. ~a gieatorthvi 10,rOL e n . ro~" t. 0osMoples hqkvwn I~Ver dow points.
~±~jV~in v nf O1Tprr.Yrt4tPi? I/P Ivreent rculad be erbstrved. ". we*S. oaduced t3 the absozrtt&c cell by adiLLttwet A &sitiaaed maowL of 24aIkIL!kO into a weal ovacustel ball which ves consectet to the ebý;U=~n cveJAtnrmian a vLL"v and a m.."rt rises of etwipper tubing. Mbe *mlvv and tukZlng
f- 'P911v tho bWglb t-o U-P sbacirption Cell wer* heated mmutlv to avcvi.-on4enaitioB In thewe Wats; the valv was t=c- :;:n-.i 2=1 A R-0 'W VA, tVM~.mL' Dite.; Use YVOV1V%&5Lj *W ke tvii sti. L-zC.'ear-r z;.:re ripeo4etI up~ 'y rentLy lo i~stl tho liquLid Jgd.
tsy cocnideri the voiume or tn. absoxpuvw.- -ýu, it. was x.a"h~Lo CalculAte VIA' ;:vdesite twat vrtudA a.. eXp~al'.4 ISC a SAvvt, T~amnLt'of liw"La Ld; If~ itua DOeUbA- tJU. 4%11 LAWe IVAP Vea* JA UWa VWp- T.attSar~ flw?.4 U.-O sdsorh.Ion am e eal walls. .lu apt case& 1, van &~13
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1/2 the v~ as waiorb.e1 on the ce~ll vfl.s since care asv taenaz to &voilCOQUGieation. If +Lie seuple vas left in the cell, tLL pr~srtý,* vms IouL4to decrease graduia.ly for r. few kholwo, thus indicatlaC that Me adlorp-zion Was occurring.
In thel process of obtaining Cd^.L% i;, umss Weidi to the B20 to procduccsampiles at various values c f totai pre~asur 166a than uua4 atmosyphlre.The daw point, ifro w~lciv the H20 partial pressura !:ould te 1stuaULec.,was ueasureit perlootically, at least ofce or twice after addin~ ftcsample of Yr. It vas rosah tnat trn daev pol- 1 r: saint o....etiaXllconstant ifth MaOW had been milned to remai alms In the cel.l maffi-clautly lcne for t~a aw.aapLium W~ be comlete beroict 02 was added.. Amajor petrtiton of the Investigation took place durln& the aiaox monthsAsen the tegrerabirm of the asborptIosn cell, which remacla near ambienttempeaui$iare, -darted by as mucb as 6 or eOC dlirtrg a given Asy. As thet~emperat-.are of Um :~eU increased, a port4un '4 '.he .4.ooi ed gas appar-ently we "driven o~ff tbo -311 vels@ sincel the &L) tartiskl &arecvre in-creaa.4 at a rate considerably greater thana roe weuld pi-sdlit = thesbasis of The perfect gas laws. The fact ~th a.--tt.as axe "'rivenofetil4id srfacer by heatfluW Is, of N 1' "n
Various coaeitigs -in We ioterItkr of the cell vpre trici In enattiar %a aecreamee We 6.Ut~rrUo; Q4"eee ~aagS& inc:maeq autamoilelacrjst,. Slyptal vanisha, azA a fUr of . acne~a pmW oil m Wavle or thoeesurface coatings seemed to hAig signsilcaat.Ly the aaiount of hkO gl-sorbeG; boever, sore *ihpw vea 4-eutzolG to WjI.jgags the cell by wevews-tlem when ýY59 of ant al--" el'etvrugs was used. Therefcre, the "JAI we*used vitt. W~e bare steel oxe."e. little dftifrai,.a. eau 27,b~v~yva be-Ween the adsorptioo of the atee] *eI! wen It wn' -~ .. 4.. j ascompared Uo IM cell Immediately ater tt had beeni awd-Illastud. Apo~rvel.ai ~m"i ". Silt I~to veil~d prbal rluce the r.lsorptia..hiu. Uthi vmLU have ta'voave a maaerab.iLe espease ead was not .=Adrode0601"%wia sine. 0%Q NPiO WW tin p"Oamave rOld4 be mo. taed.
As a result of the Inveetgatlosn of the edsorption of RW oL Uwmwells of a steel ay1IMAcr, it can be comolleded that sota~tip -a, :e~wfx~wx tom dotel~ined Prom a imesuareut a? liquid Va0 Istafatuee itathe Cell; in AC:l, waluase dol"SL±nh q?' thib eathod wuld 'ie too Uigh.In Utdt wVirk by Ow. Vaw -if I for 80 bvideb "toe AeitlPM64i '.lymeasuing Use ".! partial preami?, titane 4Z v&. ".I it. b," t~"Gamead tI"t V" V2 Partial Preassuremaruied, Comstant as O.ltweaet
uamwted of ft isa.ede &and wthe~ abeheoptl&um~ Yve edi A".&Jdm. Q&the basis of Wonwaeetigatlon of aisorptica deser..be abus~v, It sea be
cocite t&t tam VgO pe~rUak plleawo wes proba~y adof chmased bsemus.of ft 4.Iplaeiag the %G0 wIhak bsi been aioabelle on Use wall& of the ad-SWptlaa IOU. 210 CMeehet GAM11ee Of waxSL;Util n Uka the 30partilposeur. verui -ralkaMy 4ahwee im 1dempar~abAr, atrvrLu-er adsMorpio
A .ht Lave oeclArred aft.? t-1 mar"a preertv ewa measured. ~-ti t. VA M!". pwtioa o'. tee bvsgaW ) !.'W tVe W~qWVrae Vt th
ev" *.- u t neoirly r. itmaut, w,%woae a *rrur la We dotar-.:c 4.r w uscaaim _' voe.Vertz earlatlooxvs werobehly small..
1/2 the HgD wis allorbea on the cell walls since care vas taken to &voidcodensation. If' the sample ias left in the cell, the prearure •si founto decrease ra&ily for R few bours, thus indicating theai more adsorp-tion vas zccurrlzg.
I the prouo• b of obtaining d-it,% W2 ia adied to the Eg w o j .uc.tcsamples at various values cf tota. -p+•isure leon thau ue OPloiSPere.%he dev poiat, i:ron which the 42C- part~al pressure could be dateraiLOCL,wss saasured n eriolically, at leut once or twice after addin eachsampl of 52. it as round ts tle r (ow point remaned essentiallyconatant if the W had been alloed to rmain slow In ts cell PAM -aouetly 1lng for Uoe ai"%mqUwi Lo be comlete balr"* A2 ias added. Amajor pnrtion of the investigation took place during the mmn monthsWh'r te temperstu" of the absorptioon cell, which remlnat near ambientteaslaAe, varied by as sueh as 6 or dC diring a given day. Am thetaperats..rt of Wi v,:eU increaeed, a portion of the adsorbed t6ike appar-ently vex "driven oirm tho 'roll vills since the LO marti±al uresaure In-croas.4 at s rate considerably greater than one ;oU1d praict ca thebias of the perfect gas laws. 7he Met that Msiorbad meo are "drlvuoff' c414i surfsacor by beatliag Is, of rcv'rsee. i1l Imtem-.
Var•om coatings on tCbe Lterior of the cell were tried In anattemt 10 decrease the ualacrptioa; thee. c,"&Wge Aac '-eu auumbate"&cc. r,. f ypW %aralsh, wA a Ir of -. e .nus pu oi I. - e or thesesur face coat *Asa seemed to CLaWg 3nignilceauJy the amout of k4O ad-aorWl aooner, more tip* w" &-9qaIr*Ai to 'Ie-pa Le cell by evmau-tl-m viem xao of v.,*s arwý "I't~as was used. Mthrefore, %he cell veeusaft vitt. Wec bare steel. ex~eed. Little diffteri.,.;. on .bdav*e4 be-"res the adisorptio of the steel *I ube i vsa- fineIBvh ruty ase-spared to %a cell imed.itely aftr it Ma been arA-Uslal. Apsrveie is
4ta# w S..xb lliatog voLd prubeabl riuce W,: cle.rptiou,
but tale •a%.d hai - involved apieae a wOs Ar . !!,i=1sro.*eeawtjaa at%". th~e KpO par tial proaseuv could be amo. tayed.
LA a result oý the Invootigation of the adeorption or NMI or. thvlla of a steel CI In",. it cam be aamaiae tAt .w(St- -klutt ifv mnsr oe do* trained fro~m a measurawt a! UquIA EgP imtreluvsc. W4t1b. Cell; in -C3C.-Al, ve.1'wS 4%U etmied . this 109thed mld 3 too UOg.In : V-T wrb by . vslvue of .1 for lip pamplee "rex 60%rrul A Ivyaesmaa u4g %.e ua vas U&Ia pressure "efore J,, va i t. ".. Babe
"PA" it owe N20 Partial Jreeaare rer."an gosastat as differentMWASa Of ft Vale OJ404 and the &W -rpUUe YAAeV* VWM~ jteJ64M4. ()Ve hast Of M lnveettptlu. a& aOiorptica 4ear.%d SW", it us te
C1- ' e W& O Part4Au PPeamuse WU probably ash chaged DeiWneeof Rg dlApJAUWa the EgO 'ALo hai lwe adueds=6 as 9ee vai 0.0 the ad-eptpca -..-... ThE greaet owses of veiaul. in twe k4O rarta1
esaw* wor. i rosbaly oOub.. I& t lerebure, Or rAhrUr *4;drpttmo+.:rLa " oe,.red ftw.-ý tz-Max -ial ptewm v%4 oia ee..D.ar-
IV. VA W.Poticeom 0.1%e inveet~sdt~Io by %LW W"b oft -&atefr of the*;.a.i. vat newly Veusau~at.. a'.rrvfore. Ws *Ir.= the deter-
* .4 W &4"464 -. * texpertnre -aritsttois vae probebi.) am&U
Irrore arlsing frou further aalnorp-ticn after the Bpi) partia~l pressurevas maesured vere probablty not excessive uince -Investigation of theresults shows that toe tots absWol,,tlit ;!: fev zua&Aes did o D0ha 6Zajappreciably after haviov ramained :Ln the ooil overnight.
Comaison of the presont rem iltu with Laose of hBU whiic. .2veL;.e atc~ rzage of values of w and Pe inoicatad that toe Wo meta ofresults agreed vitain expecQted'xerIx&nena error.
mn~lmtal Results
Absorption curves vere tiblined for the 53ý2, ~5700, *&A 159% co-IB2 l.and& ty use uf a Perkin-E~mr ftel 99 spectroriter encloased In avtuuuia tmk vniV,, Is described in Appan&I.1 . A 14r' primU vas used I'Qrthe 5,22 and 5'(W cal bands and man UaC prism for the 15y5 can- benid.The mathod used to reumot the recorded miectaft on a linear veveumaber
acu.lc nzA to zccrur.: *tc t'±.~ ~ Ir. t~e &&mae w, that described
The dna~ man reaults. are presentead I= a mcme: :in.Ulsa to that dam-cribed in the prorriouse seatIon for uso 5tO bands. Uam of the evaireswhich are presented are based on both the present resul ts eari theMreirults. Waums of equivelent pressuro Pe were calculated f"~ masthsomqe by the twUol%~a equatienta
where 9 ute tat&L pressure doe to 22 at. pkta lirossmr p amid to
the 42 U~ the s0010
lan Pg. 11 arn owan reparerenartive astorlslin m crvoq of the 5)Ce.l W0 heed the absorpt:.an data for tWe bend ane Ved.4 in ShI. 9.fto oet4 ated unf-t..inty vf Je tabulated velues or total atsorytiou,is aros1.imatoy * 6 %a * 8 perceet for values freater than 50 =,I. Soeza.&aU.e uncesuaty 41z scanft Ssoater for smeL~er Yam"as u1ttal ab-stw.puu. iD 4Taue~uracy of the tabulated results for the other V$0 beds
DelpreaettatIvw I.ortioss of data fu.r Uis ',*r ="!, ba&.%! .'gnpttedLA Fja. 18 with AOtaL sbaýUsptin versus Pe, vwhre maca cumv oorreepeas"to a giytvalu Tht I~ V. 7 '.is Grled That. I- fttle -1 11- camwlis1 ýIt-groups 0. ftiPr~amJMl *~..Vl 0; is order t..'C p~'.the resal-t, at %twose"dIM, IN V14. 11, GA aveRage Valuta Of ! Was ebinz fir emes group ofsupea MAd the oboarved %*Imies ot total aheorptiaa vhich %r* !tl.uo &a%be table tiAu v"Kaected to the averaem v. !tw ;arrectanmeu obta~inedtiM WUat -. total abaiarption versus v atre ..̂ ch curve vas detaulnonuby tAUs VV~ute VQAAý 'Vtf to "h P;Ar ditrera..t lath lengUI, at Vhichbeach se&a I..!4MUV Vag a0'M1ed.
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298
The cu~rves ci' Fig. 1), in vbi:x1t'h i abs.rqtior veHks .~ ~nw, wc~re obtained by u~iz.Z both thie Tresunlt res-L.ts and the ýDW results.
from siri~lar rur',es Vhich wv-re ý'ray f,= .~ne HB1W date but, are not p'rt-sented in this report. lb~oe value). were tJ'en uE tv provide~r~1tfor 1.Je :urvee or, Fig. 11) in vnl1.zn pvin- i vere omitted in ordarfa.±ilitate itading t~c ctaves.
ovt~r a kee&u range or vtau.eb Qr w +2te htnii dA&.a cverlayp~md the presentdata an.!d provid~ei a convenient :ompariron. -- ce Ac-twi '..4ruud,".'e tw., ie.:,e oi d~a.. wi,,Lz_ý cznulderation for tý' ot*her sel. VCoUM havefgrc.1 Wo vit-hin 5 to 10 percent for most of thne aM.1er~nt equivalentpressures il.'jst~rated in Fig. 1P, ts well as ior the corresponding
ve 0~ b'!!ov fc- the other bar.1s. Thia ag"e'm--nt is goad whenQau ~ .z;niAzta-zc=4 ata beIng .npae rersiw- *-c~ls o
i;a.LL2 v for, ~.4.1- t'ne ac'.=racy was r---:'-.rt. Cox-psri-or cf 'lhe pý-seyitdata. with thost ohta Ini! in the ear~ly worr& of hovard and Chaipmat- was
:Iin ~s Um- be:te r's~dts r. ttW. ah-vir;tioa for sirinisa s.arplesoftet dlifferoid UY 95MU~ &uob -- Upercent.
In v..av of 'he Improved mottods vhi,.n v-4ri- discrivehi abuve, ti~wpresent resu1lu v*-. rivwen extra %wight." in determini~ng UJte poeii on.Of the Lurves c~' FIZ 1.4, vbIch are believed lo best represent ark i fthe diate; and valu-4 cbtainaed from these cu-yes aLro believed to lot acnur -ate tu. 1 6 percent. lh- barie accuracy Id ewU~t~inae rUr t.Le correipond-izg curves of other llpO bands shown be~lci.
-1 cpr-_z.utA~i.iv# aocs)rjtini, crvip of the spectraLl regi~mi near 3700CM Rre snuwn in Ifim. ýý. ,'Ine datm art llst*4i In !zblv I4). W.1ici In-cludes the van1:es or wi toua. absorption for the threoe spWc-ei inter-Vals: 2a~f).-5W~ ln'!, .Lko. - : =,.. =! taccI :=I . T% -r.=ofUSe t4)TA. .A. '- .atlr interyvelw, whizi, tuz._,COr &rareforreM ** a-% hm, 4-t1-,- R1I, tvivn I'r eanh aaxip~l. Thevalues of t~hi +PiA.2 absorpt 'un for th - V.al~. eFn vti:hcirrebpunds i. 14oi '-.1u i...m A-~ kta W report, oxv tAbulated for refer-once, by futýre vo.-Aers b'.t are L' ar=.~ in tht p~coernt r*Wst.
-iires UJ nin ? -ni t~~.V- '.tr~the t..ta~l alsnrTpt1io rfIte 371)0 ti--l ban4 wo I-, nd v, -Prpne.cy I .I.es curvia ware obtjI:-C . .'tue %.=ira ewi~&u " verý 'zi*. 4'rrzpondlw4 -.L its "or Vit 5552 fý--.
I 4.tCIk5 So.' J 2h snow IL .eproev¶., tivo ab.- 'pt i %a curves nr t;4# 1~55:mlh2C bandi. Tne 4ata are listsed !- Table JA~, tli,, ve..Asa of +AAtsA ab-
Yelp~ #A for -Lihe Rum if tro-' v 1±tt~rKlx., vh. 1.1 callad1 VAe 15)Cae keU band. The data f ir thil houid vor" treat. in tht=, -a -ncrSm wY.!r%- 'M data fcr %ne S332 :%7 tkuA 3* Qm- bwAns. 1Figure 25 uv.'~j j !WLZ ro-n -:;a o't-%l orc..i :tVa~t of the rrtbon't 4,01; to Pefil'~:.z vAj.LU-. 0! W. W~d th' cu-.-Qt *.r'# 20e~ , v11ih:1 I aet Weta&
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The self-bro.dening coeffLcienL has been detirmined furbandE of Xi, 0, C2i,, C(•, an "r.i 80fi nt.niach i: 0.flrued"In "C tcli.y f ....... I . ...
abo6urbing gas wi Lii respect tc N2 . By the use of the e-,erimentallydcrtermirpd 3ýfI-Ib Cr- cnng it~e 6'i;ekrt
equi--alent prebsu-e Pe wbich served to sipl±_.; the anilysis of th.data by accounting for the bro&Aening by the al'r;orbing eas and by 92
1 'h Lý.e use of a singlL varieble. Values of 11 used ia Lhe ;'•-•lysisrf all the band included -n the present Ye6at.u cl<i.m Ure -in Table 1.
The relative broadening abilities of various inaitive gaseb havebeen investigated and, where possib]e, the res8.'e. he-,h bhen nnmparedwith those of previous workers. Tha iebultz ix - in Tables 2,3, ana. 4,
Absorption curves were obtained from which the total absorptionhas been determined for the N2 0 baAls au 2565, 2461, 1265, 1167, 692,and 580 cm"I. The data ere -I.ted in Tables 5, •,l ud 7, and curveshave been drawn to show the functional relationship oetween total ab-sorption and the two pare.meters, absorber concer.tration v end equivalentpressure Pe. Values of the band intensities of piLrL at"" ihtie bal•bhave been determined. and compared in Table 8 with the resuits reporteiby other investigators.
Total absorption ;madurempite bave mi.so been made fo, t.n . ba~nlO -
at 532, 3700, and 1595 cm-i. The results, wh1eh are p';',cr.ted intebuiar form and in grspoical form vim n _,,.t*l tIp4ur;i'on plotadagLitnst • and against Pe, suppieimnt eurlier work by jiownrd, Bur.:b, rn.•.
WilliqmsA, and serv. as a check anianst the resutL8 of Lheoe wurerafur values of v and Pe included ir both. There is good agreement be-tween the earl..er results and the r'es',nt results, which werenhbatno* hv 1.,roved mt thods.
312
.1. Dwarrl R. Burch ano' Dud3Ey W8*ia..,t .ntific N-port. 1, ý.'.o-pbki)oec Research Diroctorate, Contiact No. AF19.604)-2633, AirE~aearch mAc Developiment C-mad Laurence G. Hana,.c Field,Bedford, YAsacehusetta.
kDarrell X. Burch, David A. Oryvnak, omd Dudley Villiamm, ScientificRtpiL 2, Geoph~mem Ateaueuch DJm~ru~oate, Contract No. APl9(6OJ4)-2633, Air ritiwmrch and Developtent Ccnm~ud, .Lmu-ence 0. HansocKrield.. Bod-ford, Psea.ct~ufetta.
3. Adgar B. GUng1et-o, Phb.D. 3.isuertation, The Ohio 3vae Ukdiersity,(1958).
S 4. Dar.ell 1. Burch, Pha.D. dismertation, Ile (hio State University,(1959).
5,. J, Z, Hoverl and R. X. Qmyazt, Engineer Roncarch uad,z DevtopcmntLaboratories, Contract V*4099-4mg-4I0O with Mhe Ohio Stkte Uxaver-sity Bn tar 7o.nation, Report& 18, 20, 23. (1909); also flU.-Wie State Nhaeerh VWanation, Contran L Di..313-099- l-k, Report
go, !a (1W5), and d. Opt. Soc. Am. 4.2, 425, 8316 (1952)
S. LT . I toard, D. 1. Buza, and D. Willients, Geophyuicval ResearchPapar go. Is0, aRD, Air Forc~e Cumbridge Ieaeeroh Laboratorie. (195.3).fee slIm1 J, Opt. Soc. As., 4-6., 1-M, 257, 2's2, 431: 4s:2 (1956).
7. R. N. 2ood,- and T. W. Vaormell, Proo. Roy'. Soa. A. M, li.(8 (1951).
d. ?'. C. Crose eutd T. Thnuo!.;, .. Q.a ~iiys. 2, C (1934~).
9. D. K. Edwards, J. Opt. fiv-.. An. yt, 617 (1960).
10. Hý Namlr, J. Opt. Soc. An. ýW, 2X2.- (1.960).
LL. x. r. vaslievalcy and Ts. ri. Napnrant, Opti r and R ltrAr.~y, Vol,
vii, No. Is, 3;3'(1959).
12. J. Izatt, 'AI.D. dlavcrtmtlomý Iho JTohn llopk~a U,.1varxity, (1.960).
13. W. Benedict, (Private ecanm oalietiO).
1.4. W. Asses.?. and T. Ilder, ?P1ys. r.ev., 21, 3083 (ly5).
11. A. N. Therndike, A. C. WCL1s, and 2. 3. Wili'',. 3. Chan. Mrsa. :U,
lt.. D. V. &Moers,, Jr., mid S. L. Crawford Jr., 3. Chat. noy. 1,, 1%SIs(1951I)
3 13
A VACUUm TAnk FYR A- PRJKfl-EIx=.
The rwrd. evacurit ;.g Vie OptlelLL pat~t of' sprctroz,.-ter usedfor inve-tigitinq stroi~ tm~citzheric absor~pti;)n banids van dis..ueeedIn Recport .1. &zicloalr.n the rerkl.u-ZJiukei Hi4t1 .21 v.ýle-ibeaa mpero-meter it, A V.1"UUlin Vol, 1. e ) .d o t e impra±ntica.L; t.herefore a vacuuml~ank war. desig.ned eLA14 *xrnatructed I.o contain a Perkin-11mer ?~de~k 599
cnzý :--oeam o wim-romator, whi,_h was mw~ '; -be 4 n th ! 'otbcratory. '7.t 1itMik, Which Is illustrated !n P;... 2V. is L[Lu-eia bo.
and by its veraat'.111ty. sh mir. r or the tank convists of a placeof 2', -11ncL v'av. 3teel. pipe vitt /~i~ tbl:k valle, and the emý VpAtesare circ-ulau- 1-"cex oJbV-inch thirvi r'eel ;P~at.e. Tht nonocbrnuatorac&u& i'.zutir cozponen~v -l ýx.z an '"l..-Wat..t -&.,,h' Inspot-vel.ded Inside thie tztnir. A pvrtlcr cf the toop of Lav tank wasvut away .ini the hole co~vered by it lid of' A/4-irch thick rulexiuglass,which makes it yommible to toe all. the enclost-d parts. An endleassniect- of pure gum ruabhri .- r-1 beir,'s os a gaskvi. letweta the lx2asmi~d the steel. tank. Pubber channL.1 gaskwtc pravide seals 'betwmen t.w
ts.4ý %.1. $Al :1 4S.Ia vial. piotaLa.
31ecctri za. e.xvn~'aticub "r 3. rcvIde' throughk ber~sti cally seal"dporcelalln ýittlngb Nu order to avoid excessivet noise whieh uagbutsitrio free a fitting in the eirriut oetveen the presislifier and themspuifer, tLc ccL1 c-nzn-rt'r. t*;5P Vw; v...at ac put throudAi abalt in the end-pl.ate whl1cb could~ easil~y bw sealed vwlih a putt~yUkesea1±aW comound. 'Ni~s uttblo vas cco..red with an alr-tljýL plaette.!vwtkg; bu,,t '.wts a._-zXiBkry L, open Laie pliieti: c.AtID4 Nad phi. WotVax around thie wirtu in tW, tois* preront leakage theougi tbP cablefrom one and to. tjue other. It. ohould be noW~ that small leeuka can b~etolerated mince the vacuum. ptii. Itl:ft fin duir'. op#Alotion 'f~ the
Mchni4eal. adlumiauson, can be ma4v through tunc of tU.rrr "rot~ati %gtivala" s..I' Of 6 P'.ele C! t-LV5 AýC.lt via' wsý a%)I4ce'd .. icr 0Lhiin the tank and drifloi th"' Y) to af-.:Ppt as piece nil ý1/8-inch drillrc4 A --Ircular groov* wias machined -'it of thw tmeý- aurrtace of %At1-raka piece to hold a m.2.I. "0O ringE tt; forms a meal around ttw trillrod. 1the. seals wer: (ui~.4± to be virtualUy loan. proal, ar.1 Rau itpopulble for adjuctmento 6i, be .ja~i. 6yj a *.tatlnit muLLun or b~y a linear
=W Il , slilLng thy rod throu.o :1., -ti. '.he whnleal coluiictioeswee.. -- d te, awtko trii nro" Ovi . vC the mirrors, t' ?np#ral- rA onuttor
-t's ttie -ntsne- alit., to operate sk watww on a sgmal i-orrition,I "!i' rr.o epiltt, w.W~ t,, -L-*.-e 'he Littroy %slrrvr Thu gear
bon ?.MCI .y,;tcm for tht itto di 4. wav. *vuovod' from the
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a nler-z' of cupo tub. ing Uzreh v.-Atu,'1 tr-, 2: ath -t! :cr tranc -=It.
t~~~~~e0 "oeo.~. Te t-..he t~esrt~ ttulw -p.ALL 1.ate tre uvvr-A
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vaA n:2 cmirtnifled im o trwha~the hrm~otari LcnweJ lu forw Igi rrn theg~t~loer analIotatnl Sv ist- o-ngfea ity v is swlia)3e duringe Oere
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