The solubility of solidified toluene in liquid nitrogen

A method of determmmg the solubility of some heavier hydrocarbons, whoch are slightly sr#uble m liqurd mtrogen, ~s described. The investigations were t a m e d out by a eombmatton ol the hltrahon method and an analyttcal technique for ultra mrcrotraces determmatron (enrichment and gas chromatography wtth mass spectrometry). The solubility ot sohdHied toluene m hqutd mtrogen was determined at 77 4 K. The exper~ mental result, 4 45 x tO 8 mol traction, was compate.d wtth the solub/hty calculated by the Preston-Prausmtz method.

The solubility of solidified toluene in liquid nitrogen E. Szczepaniec-Cieciak and K. Nagraba

'T'he dala ~n the solubdnl~ ~I tlvdro~.'arhons m cry~gernc liquids conCelTl sl)hJllOns Ill hquid ~xygerl "~"wlln~.'ii is die cryugeruc solveriL trlvesLlgaLed wllh L:,realesLaccuracy LIp h~ re)w, lhe s()hJhihly in L(.).., ul ni~m~ lharl li'~l)subsLar,ces ha:,, been delemlu-led, nneludmg more lhan 2() liydrocarh(ms, whi~.'h are .ga'.;es~)r hqutdl,; In ,.~rdJna.ry c~mdililm.',,

prodw.ed by Chemi,.'al Planl ()~wtecirn, hquid rlnlirogen was obliamed by ~.'orldensmg gaseous nnlrogen Irom a cylinder Oxygen was removed by passing Ihe gas Ihrou~l a ¢ohJmn c~nl~urunt..,, a Leuna-Werke ruckel ~.'at',dyst t~':,2':, and Ihrough L'~)hJllins c(mLanrunF..,,a ln~lecular ('aA sneve h~ rem~we waler Val'.~ur and earh,arl dluxude

'T'lle lllleresl Ill hqnl(l ~xVg,en aN a .s~IvenL lur ,~rganlc sub;dances i,',,well itJsLnl'led by lhe cllemn~,.'al properlnes ol ~,yl,,lelTl',,oxndn'zer l'lJe], which are lurnled hy L.(),., wHh

'T'he ,,,,aluraled soluhon ol hduerle Ln hqutd rlnlrogen was ~hlaJned by dropping toluene mlo a dewar Ilask with hquld ntlr~gen 'T'he s~dulnon wan mlensnveiy arid repealedly ,dlrred wnlh Iheelecirncsltrrer The prucessolsalLuralmg did nol last less than 24 Fn~urs Dunng the LnlervaJs in slurring, lille dewar flask C~)lllalnlng lille s~iltill~irl wan slopped with a ruhher sh~pper, a tube eontaJnLng a,,.'hvialed z.eolnle 5Awa;,taslerledln {lleslopper Ze~)lile was used toprulect tile S~ILIti~m agalnSl lhe erlvlronmenl',d rnoislure and carbon dJoxide

L)I galll~.' ,~iJh,',;l a n {'e~

In c,,ullraM, hqmd ntlr~Lgeri I.',,a sulvenl whnch has heen mve~,dlgaled only parll',.dly. 'Tlte ;,~h.nbdily Irl lhns s(dvenl ol ab~ul 2()gases, trlchJdmg 6 llglll hydrocarbons '~'4 , has been d e l { ~ n l l t n e d l i p [() rl(~W E'.sllnlalnm" ol the s,~hJhlhlv ol hydrocarh~ms m L.Nt has sil~wn Ihal ihe e×perled values I~r heavier tlydr~.'arb~)ns ~fl alkarie series, slar[irlg Ir~,n he~,'.alie,artlmalll' hydr(~ ~.';.Irbllrl,',,,arid ~.'yd(vaJkanes sh~uhJ be very h)w, ne h~wet Lhan 1(I '~' in~)l Iraeltun A c~,nhlnaln,i ~i lhe rilLralnm melh~)d and lhe analyltcal lerhntque h~r ullra trltct~drace deLerrnmaltori, ennclunerll and L.,as~.'llr~rnah~l:,raphy with ma.',~sspe,.'lrornelry, wa:, w{*rked qllJi lot lhe .s~hJhdily nlweMtgaltori.", ~1 the ab~we i.~,r~lUl~ ~)I ~.'~inl',)iurlds 'T'lle rlew inetli~)d was used h) sludy Illl" !,iohJblhiy ~l sohdnrled lidlnene ill liquid ntlr(l~,ell

Experimental details ]'lle delernllrlall{~rl ~)1 rile .,~dlJhdily m liquid rlilr{~gen ~1 ,,~dtdlln.'d I,,duene hy lhe I'lllrall~m melli~d;, eon:,,i.',,led ~l ,~allirall~m ~[ hquid nlir~geri wllli l~liuerle, !,,eparalt~m ~)l the ,.,aluraled ;~luln~rl ,~I l~hJerle nrl liquid rltlr~gerl ir~ml lhe exrv',,,~ ~I !,~lldnlied l~llnenI' l'w lillrali~m,evaporaln~m ~I h,]unJ ilili~gen Ir~un Line ~i(~h.ill~n, qlJanlllallVe delerrnln alllHi ~1 [he Ii~luene ~l~li~.'(.'rilrall~)ri fn aL'el(Hle sl)itJ[l()rl hy (_',("-MS melli~,d The l{dh*wuil:, rea{ larlh., were used irl tile C()IJri~,L'ill lhe irlve:dlgall~li:; l~luene Speclr AR, pr(~dlJred l.w BvkMallim.'l,.ri,Jl li"lleni Pr~,Jul,.re Cimhll, irlelhyh.'yrhdivxarie ')')' i, pr~)dm'ed hy Fhtl,,a A ( ; , Bm'le., S G , a~.'el~me pa. E 5 - C ~'* with Ihe (':rvu.qPrll,: DPparlmerll ,.)1 the In,,lniulPq~l ChPml,HrV, I,)qli-,lUllnl,,:ln Urll%lPr,,lly, ul I~i,rul3rtlq'za 4 [ , J()-(')6(.) l~rdhi'lvv, PIII,.IIII'I, I~, N i,, w l l h [he RPI.]ILIrI,I] Ldbi.trdlltry i~l F'l'ly,,iq,ll l.l'li~mtl dl An,-fly',n', ,.,rid Silul'lur(-' Re,,earl h, JaqtPlh~rm:Irl UnlvPr,.,tly, ul I,,, rUpllll' z,J 4 l , ,.'I()-l)l~ll Y,,,rah i'wv, I='~lldl'Id R P r e l v , d ~I] Mdy 1971.'I

CRYOGENICS

OCTOBER 1978

In ~rder I(~ separate the precipitales ~I sulndJlned l~]lJerle the s~duln~m was l'nllered lhr~u].~| a tube, prevn~usly c~oled wilh Inqund nilrl~gen, arid equipped Wlth a .'.;uiliered glass Filler. aw.-rage p~re dnarrleler ~)/J. arid a slyr~flo:un nri.,.;ulatnnglaL'kel '['he hltrale wa,,, ¢ollecl~'d ,n a glas,~ Ilask placed in a vessel wllh LN,z*' Aller Idtralmg a required arnounl ~1 solulmn, ll'le ilask was .',d~l'~ped wtlh a ground glass sh~pper having a l l i b e ~.'{mrle~.'led w n l h a ga,'.;onieler lhl~,lug.h a val.'uuln tape ['tie wdutne ol evaD~raled nllr(~gerl wan measured w l L h IJle l.:,,a.,,;~uneler Al'ler hquld nilr~gen had ,,.'urnplelely evaporaled Ir~nl [he l'lask, llle re:.;idue ul l~hJene Irom lhe flank wails wa;, washed itlJ[ I-'o do flu:, lhe f'la.,;k was rmsed several limes wilh kru~wn volumes ~I acelone ~.'~m[aJnmg a kJlOWrl arri~unl ~I i.~ slandard le rnelhyk'ychd~exarle 'T'he acelone used h_)r lliiSlJ'|g was rolle~.'ted m ~)n~.'vessel arld ~..'(irleenlraled I{~ I nil Tile acehme ,~,()liJLlq~n ill ll~liJerle with llle trilernal slandard ~d'daJrled m lhns way was iJ.~ed dire~..'lly in quanlllalwe (lelerilitrialt(~n T'he d e [ e r r r t l n a l l ( m ()1 l(~]tJerle ¢ ( ~ l l v e n i r a a l l ) r l w a s ~.'arned (H.I[ lJSlrlg a gas {,'llr(~iTial~,~[~,ra[~ll

r~,tpled wnlh a ma~,,sspeclrolneler LKB '-~()I)()S,equnpped wilh art a~.',..'eleralni[..,,wdlage ',dlerrlal~r, ava 'z The ava wa~, adjusted Io regisler illrih with v',..iJlJeSol ,'n/e = ~-)I (lhe main peal,., m the mass spe~.'lrum ol L~duerle) and ,'I."l (Ihe nlain peak In the mass spectrum ol melhylcyd~dle~.ane) The mass speclra ~I l~hJene, 'T', and rnelhyh.'vd~)llexanle, M, are ~,,h~wn in Fig I T']i~.' resull.s i~l the mas,'.,.',,pe~Ira, 'T', arid lhal ol the internal ~,,larldard, M, were ~hlaJned I lhe energy ~d' t~ruzLnl..,,elvclron:.; '70 eV,

LI(.)I 1 -2275/78/IO(J6[)1-03 $02.00 (,-~ 1978 IPC Busme,;s Pre,;,~,

601

I()(I1.~*, r_ ,+,, ("~() 4() L )-

i

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31 )

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~

41 )

II b( )

I()(I -

J

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I

hi)

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I( ) "~L

, ,r., '-111 It )( )

Ma% ,,l:)Pi.'lra of hJhJPrll,, T, and rrlPIhvh.'yi.Jh)hPx,Jne,

(i

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I"111

()()'4

i, ~

,~

'P ,''

.,J,

711

Ih'

II;' ( )

, ( ) 't~,

I

I

,,.,,,, .,11

%11

""

Ill ?_

I

:;'- .hi,, 1

f,( )

I

IJ

MP II'wh.)l y(.I,*'jl ~h(":~.ll

';" 4 ( ) -

F=q

i.II

I

,ll,

T( lllJ("l IP

I t',(

1~4

I

)

I

HI )

I I .,lll uhlh'd

I _ _

I( l( I

I

I;.q)

141

[, P, ,1~,'"

i I

~'h.flul:.hly

i.)

I,tlt,/ll/m

b

r.IH.:lPn,

u~W:lPn .rod mPIhanP

=

N

',xI)['T'l

~- () Iq

(I)

Where lilT i~ file liei~ll ~1 Ihe lwak m/r-' = q l , T', IV M I~ Ihe hei~ll ol II'lu peak al m/t' = 83, M, I rl ,,,, lht, h4u~ne concenlrali~m glVell irl pl or h~hJene In II) trll ul uceh_me

LI ,./I.)

t~

l'rl

iiii III idd~ d

~__

m hqutd

'T'he equatl~m ~1" the raJtbraltlm curve ha.',, the Iortr!

f. L.'I

E

ol lulu~nP

h~luene c~mreritraltons Irl Ihe rart,t.,,e (I f)~l p l / l ( ) t n l (~l acellme-().,.-I~ pl ~1 h~luene/l() ml ol acehme, Ftl.~, 2

,,"~" ,,'"'11

o ,,,.".',6

Ftq :1

--

W'r

U U,-':

(,'.)

N 581.1 IV M

I

I

I

J

I

[

~'1 lye,

(.1 IL'

I11H

l) ).'4

I1 3(1

l) 3l',

I

F"qualt~m ( 2 ) de,,,;crtbes Ihv relalton helween Ihe I~hJune c~qlcenlrall~m, tn/.11 uI 1<4uerw per I(J ml ~1 acel~me, arid I.l'r./ IV M

1142

[(JhJPrlP I fiN( t'rlhl]hllrl Fiq 2 Relaltori1~hip bPIwt-,en IuhJPnP (.:{)ncPrilrdltOn arir'] IhP ralio ol Ihe IoluPne pe,.-Ik hPu:lhl (wllh rn/e = ~1, r), hi Ihdl I.)l melhylcyclorlP~ariP (wiIh m/~a = 83, M)

2. Ihe lernperalure ~)1 the ion N()lJrce 2~()"( TM, :1 the [ale ~1 Ihe .'.;can 2111m .,,,-t , 4 Ihe acceleraltng w~llage ;l~(lll V,

Behbre illea,,,;urernertt~,; ol the soluhdily ~1' Ioluerw m hLlutd rulmgen art' made, a c~,llrol delennlrlullot¿ had been yarned ~q]l m p u r e I,qutd nilr~=~,en If did n~H .'.;how presence at h4uene m IN.,. Results and conclusions

'T'lic re.'.;uJl.~ol Ihe '.;ulul'ulilv deterrritriali(Iri.,,, I~r !,~4idirted h,luen~ m L,N~ ;ue gtw'n ,n ruble I

~, Ihe resolvmg p~wer ul a spechurneler I(1(.)() The condtlt,,m,s Ior ,separation ,Jr the suhslam.'e,'., mve,sllgaled I

Table 1. The resulls ol solub,l,ly d e l e r m , n a l , o n lot solidthed loluene in LN:,, al 77.4 K

Lhe column 3 m hmg arid widl mlernal d=ameter "1 ram, I'dJed wHh 5% SE-.:I(I on a chr~rnusm'h W t,l.l/g(.I rnesh,

Volume of rulrogen (m ordtnarv corffll honl~) evolved by

Ihe earner t.~,a.s,hehurn, rale ol I](~w I() rnl n l l n t ;

Sample number

ol ItllralP Vo , I

WT WM

10 ml ul dcelone

T()luenP, ,:,uhJbiltly m LN:,, XT Irr, d ItdL;lllml

I

18'12.1

350

0384

447x

2

17553

3 I0

0.339

4U7 × 10 .8

3

1269 5

2 60

0.279

4.1j3 x I1.)a

4

13660

2 78

0 3()()

4 6 3 ~ 10 8

I Ihe cuhJmrl lemperalure '7()"C, 4. Lhe m~lecular .separalu~' I"iU"(', 5 Ihe I]ash healer temperalure I ",(I"C', b IJle mleC.hon w~,lume I pl (~1 acehme ,',4)hJll¢)n Subslanves leavmg Ihe chr(~matugraph were tdenltl]ed by c~rnpann~ Iheff relenhon lanes wilh ltm.',,e ~hlamed I~r Ihe pure c,~m~pound.~, h~luene arid nwlhvlcyvh~hexane 'The cahbraliorl curve, Iv Ihe curve i~l' Ihe relali~n.,.;llip helween Ihe h~hJerle corlc'enlraliun arid lhe rali~ ~1 Ihe I~lluerie peak het[~l lo Ihal ,~I melhvh'ych~hexane, wa,~; delermLrled by n)easunrlg lhe peak height,s ,',~rresl~mdtn ~ ,. h~ nt/~' = q l , T, and m/e = ,'4 ~, M, h~r I'~ !;~4ulmns wilh

602

TohJerle (.:on(.:Hn Iralmn,

evdp(.)r allot1

pl m

10 -8

'~T = 4 45 M I() -8, ~"T = () I,'J x ILl -8, ;t T 'T" ~"T x tqE' = (4 45 "T 0 4 2 )

~ IL) "8

CRYOGENICS

. OCTOBER

1978

]"lie anl, uJnl ul t'dtrale laken I¢1! analysis c~lrespunded lu I ~()()-IX(I() I ga,;e{)lJS nllr~i~,erl irl ¢lrdlrlaI-V t.'urldlllOllS

The whJe ~ll !,tlhJhnlnty llll ,~ohdnlned luluene in L,N~ n,~ 4 ,-15 ,~ I(_)"~ rn~l I r a r t , m at '77 4 K, which cuire,',p~md,,, lu I 17(1 ,, li)"lg,~d Ii~luerle lur I I ~ll LN? T'he experimt'nh.II resull is ,',,Int~lllv luwe[ than the s~lluhdntv .'alt:ulaled Ir~nl tht' S~'at~ hard Ihldevrand eqnatnnn, nanlely t~ I,-I .,. I(.1" nlul Iractl~m "

The aullum~ are gratel'ul Io El~bleta Palunek and Elzbnela Lamch I'm their help in the measuremenl,', The work was sp~ms~red by the Institute ul Low Ternperalu~e.', and Slruclure Research PAN, WRI.)I?L,AW

References

'T'he expertni~-'rllal and calculated ~dubllily values I~l !,~hdllit'd h~luene irl hcluid niln~geri, ~xvgen and methane ai~' ,,lu)wrl irl Fig 3

I

]"lie exl~e[irnenlal dala have heerl used Io cah'ulale the It,, r-ldlamelel I'll[ ;~uilJllun:,, ()1 I~lluerle irl hqLIid tlllll)gefl and ntelhane ~ The Ir~ paiamele~ is 11 LK),-1I()l the s{|lUllOn nl I~duene in LN, and () (14 h~r thai m methane

4

The ',l~hd:_nhlv ~1 Ioluene Ira,',. tile tughest value Ior hquld melhane snlutluns and I~)wesl vahJe fur liquid nltn~t.,,en '~¢lliJlUlilS (llle dlll erer,'e is appn~xmmtely three ,~rdels ~1 Ina~?,lill Lide )

7th International Cryogenic Engineering Conference 4-7 July 1978 London, UK sponsored by the International Cryogenic Engineering C o m m i t t e e and the British Cryogenics Council. T i l e I ( ' E C '.;er.~!; u f L:un/er(.-'r,.:e~., ll~h'l ev(.-'ry Ivvu y~,ar!; [lav(-~ rap.::llv ehlaLll I~;t,-,d tl lerTit;nlves ,.~I; a rrhJlnr e,v~trl/ Ill I~'i(-I {:dlerld,;ir Ol Hve~ry(Jrle (:Lirl{ ;~1' r i(.-,d w i I h (.:r yc)~ngl rl .Her lng I~(.;~lrlL,ll ij!.]y T h ~ 71[i Inl~rn3ll~)n;.,-iI (~(-)rlter~nc~ agL,-Iin pr(.~Vldi-,r] ;..trl e×L:lllrlg c:r(.),..;!.; L,~c:ll'r.)rl u~ l h e I;:llel;l ru!;Han.:h irl I[lil; (.;urlt;lar~tlv dHve, l o p l r l q t~eh:l a n d wa~.; IhEt.. too'3| glJ(;L;esshJt t:untererlc:(e I lehJ Io da lie, ,-II Ira{:l Irlq !,on'ill 4 F.)(.) d~lttga h.-,~; from 2!.-}~.:lllJlllrne'} Lur~h-'~enr:e w,~, ur~ l h e p r a c t i c a l

CRYOGENICS. C)CTOBER 1918

applu.',al Ic)n~;

1 "~

McKinley, C., Wans, E. S..I..4d',an Ct~,og E'ng 4 (I~J6(I) I I [N'ni~enko, G.F., Faln~,lem, W.I. T'echnlka b¢'z,opasln.,~ll prl pl{~llW{Id,~lwl~ ki~lulnda. M.~kwa (19h8) Bulan~.,M.(). ,I hlol Slrltt't 19 ( 1971) ~9 Stcz.epanlec.Clfcr, zk, E., [~browska, B., Wolla~.ek, Z CTm~dm~'t,~12 (1977) I Sz,t'z,~t:l,aniet'.(.'ll~t,ia.k, E,, D~blowska, B., l:apn, J.M. Ct I,ogemcs I 7 ( I q 11 )

6

'7 H

Szczepaniec.Ct~clak, [:., Wujlaizek, Z. Pr~.' S[xlh InlelmJl CIVOg Eng Cnnl, (;len.hle (197h) Holnul.ledl, B., Palmel, J. .I ,4d~,a~l B~t~'hem P,~,Huq~harm 7 (I~'11) I Kulala, F. Re~e~Jlch Rt'poll, (.'~nler t'ol Re~alch, Inc L,awience, Kansas i I q'l'~ )

ut c'ryuL.lerl,:'i, l l q e r e b v t u r t l ~ e r l n g th~ uru:llnal ,:IIITI (_)1 file L:Lln[eli-'rl(:Hfl w h l l : h \Nd% t(J L:I'I.J;JIH ,:lrl I l l l ~ r r l a l l ( . i n n l 1, )tutTi I[i,:ll w n u l d !;I irl'luh:ll~. irldLl!;Irli:ll illl~rl-,';I iii L;r'y'Llt..]~rllC q-~rlq.]lrlL=tffrlfiq Man-, tll,~n I (.)(.) p a p e r ' , d r , repr u(hJ, :e~J in II lu.; vr)ll irru_-:t c, )vPrlng tt-u-~ ,;~_!~!jl(.)rl drld irl\/ll~L] [)~j[.l~er!, pl (e'J~.rl I(-~d ,J I II I~-e.(:rlrl h-,I ~-'rl(.:~ t u!.lHII ler v v l l h ub',llac.l'; u l l.),qJer'; qlve.n dl t i l e pq ~'_,l~r f~H!;l;IL)rl'., r(~[m_:!;~'ovHre~J Inc:lt.lcle c:rvu!..]L-'rlt~:~; in ';t_),_-IL:~.rH',F~arc:[i, f;IJ[lHl(:L)lldlJL'll[iq rrlJqrlL-,ll;, c I V r m l d l ' ; ,:lrl~l ',V',llenu,, !.,uperfluld he.lnJrl~, c./Vr)(.]~rll~:f; Irl elP.(:Iru.:al L-.nL.]~r~eer~r,.~, mdu~JIr nil ,:lppll(',jll()ll,.,, I~eal lrar~:;ter irl tl)H ruldll~u.1 IrurTle, rHtru.]Pi a l l u n , tnul~ ,]1~ :al h~ezlrlCl, t l o w dyrldrTI I~ :f;, rrlalerl,jh; pr ( )p~-'r I I~.S, hH,"l I [ rarl~;le~l, ',u[.)t.J.r (:()rldl.l(.; II rl!.] fTh-111:21h:lT!; [.)r~l.)ara I lur~, irv;I r LII'TI.~rl I i:t IlL)n, !;lJ [_)HI I.:(.)[ Idl.l( :l I[1!:1 ~:(.)11CJlJ( : h.)l '., T I',.-'~,e pr n c e e d I r,..}u p r r ) w d e dr = I-~';'..;Hrl I iJI drld up In lh(~ rrlnrlute r .Ptelerlce luc)l h.)r all Ihc),.;e irlv~)lvHd in I(-ivv luri'lp(-'rdlur(e (.-'rl(..]lrl~(-e.rirl(..] a n d re';e,,~i(,h M a k e ,..,lure u t y(.)ur ~:ur)y n o w October I978 650 pages / illustrated / Cloth I P33. O0 net ISBN 0 8 6 1 0 3 006 0 Ava#able through your usual bookseller or direct I rom

IPC Science & Technology Prer~ Ltd., 32 H=gh Slreet, Gulldford, Surrey, England GU I 3EW Telephone' 0483 71661 Telex 8595568CITECG

603