The Phase Behavior of the Methane-Propane-Pentane System Citation Wald, George, Jr. (1939) The Phase Behavior of the Methane-Propane-Pentane System. Master's thesis, California Institute of Technology. doi:10.7907/3kym-qy27. https://resolver.caltech.edu/CaltechTHESIS:01072025-181637917 Abstract The compositions of the coexisting phases in the methane-n-pentane system for a pressure range from atmospheric to 2500 pounds per square inch at temperature of 100°7F., 160°F. and 220°F. were studied. Coupling these determinations with data from other sources, gas-liquid equilibrium constants of methane and pentane as well as dew point specific volumes were calculated. The composition of coexisting phases in the methane, propane-n-pentane system for a temperature of 100°F. and pressures of 200, 500, 1000, 1500, 2000 pounds per square inch in a range of ratios of propane to n-pentane from 0.05 to 1 was studied. From these data, values for the equilibrium constants of methane, propane and pentane were calculated. Item Type: Thesis (Master's thesis) Subject Keywords: (Chemical Engineering) Degree Grantor: California Institute of Technology Division: Chemistry and Chemical Engineering Major Option: Chemical Engineering Thesis Availability: Public (worldwide access) Research Advisor(s): Sage, Bruce H. (advisor) Lacey, William Noble (advisor) Thesis Committee: Unknown, Unknown Defense Date: 1 January 1939 Funders: Funding Agency Grant Number Standard Oil Company of California UNSPECIFIED Record Number: CaltechTHESIS:01072025-181637917 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:01072025-181637917 DOI: 10.7907/3kym-qy27 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 16947 Collection: CaltechTHESIS Deposited By: Benjamin Perez Deposited On: 13 Jan 2025 22:31 Last Modified: 13 Jan 2025 22:45 Thesis Files PDF - Final Version See Usage Policy. 20MB Repository Staff Only: item control page

Thesis by GeQrge Wald :tn Partial Fu.aillment of the Requirement £0.r the ~ gna of Master of Seienee Ca.li.t'or:nie. I!lstitute o1' '.l¼)chnology PaaadeOO..i! California.# 1939 Ab:atl'aot '.!he eampositions of the ci,oexlstiil,i;i; phe.s~s in the methe.nQ,,iti n•penta.ne system for a pressure X'$.ll$e from atiooapner1o to 2000 pounds -per square inch at t.empera:tures of l00°F., 1609 F.,, and 220•,. vreJ-e S 4vlldiecl. Ctupling these dete:nrd.na.tioru/1 with data from. ether aoureef;l., ga.s....Uquid equilibriutn constant• of methane and p$ntru"lo as well e.s dew point epeeifio volumes we~ ealeulate4. '.!he eompooitien of ooe:tdattng ·phases in the methtUie, propane D,,i!>pentane $yetem to:r a tempere.ttU'tlJ et 100.,.Ji\ and pressuN}a of 200., ooo~ lOQQ,, 15001 aooo pounds pet· aquare ineh 1n a range ot ratios ot propane to n•pentane fi-a:ra o,.05 to l 'WB.S studied,. t;-om these data, values tor the tHJ1rl.l1brium constant$ ot U1:1the.ne• propane and pentane were oalcul~ted. Sf.n•· t~- ~potl#at.h11 ot n,4roqa'°bo~ oeeUTe ~t •ll a~•• of enido o.U. p~4,uotlon, a ltru>Wlecl- of ve,po-tlae.tlt>n charaet4ri~tto,- et hy4ro•r'bQn inb:ture-t· f.$; of patti•ulat tntenst ~ pet~i•• p~ tucttou and p~oe1$lil&i 11\e appl.icatlea of the ef¼µlli,'l)n,,- otnettu1t$ pn>poatd bf S-ou4e.-a.,. S•lhellner anll iNwn to: va,p0-J1.af.litlen • eh~a¢te~ isttot hae ~ to~ t:o \le the most Ju&table• By d•f~tlfxtt th, gq•Uqld.d etu1libr4.um Cl).nJtant i• the- i,ati.O tf ~ • l • frtotJ.011 of e. e(MllpQnttnt in the ie,S phase tQ i~EJ Jnlll~ fre.ttion 1- the ~0$14.e tuig ltqu!.d pa-.-. 1 math~tteally •~•sed u K • - iT wh•n K U- the equ1.U,bri,1;1l.1); e<miMnt• Y i:t the- :moi• traction of the coxapone.nt r,t the ijO.S ph-.~, !,. ie th~ ~le fraction ot the ~r;,n~·n t u the liq;utcl ; pbe.ae., lt ee.n \le $8.fJn fn>m the abov~ dettni Mon that Wb♦.n gi,.?l a kno:wl.e~ge o.t the e~peJitlon of trut ph..,. and. th, vale ot l, t.no eompoei t!Qn ot the o.thel" phaff •Y ~ ft.leula:ttd a.1.-1ctl;y• the tt~•t consideration ol, equilibri-wn constant• 'b,Y sc,,at,,,,_ S.l.ht~t au<\ Jro-•()J end b'f xat, ~ lnwa\l) wat theoN-t ieal. f.n ~tui"$ l;>itng •~4 mabllf ..n t'he utnJiaptJ.on of tdea.l ~l,u.t-ktu, Wit#t th.f.t ll~veloJ?Ulient ot aceurato .methlt4s ht ~ f'Ulal.yei1 of hy-dtoear•n ml•tu:re'IJ • notably 1>1 lt$e ot a .low+tQI11.p¢fttu.re,., l•w..pree~ .f~aeti(.t~ ating ~l~r~ dtrri.$e,j lily tc4'btoln1ek (a) .- ~ lllinlple prooe.!lure ft>r fUl • •-t •n:t.•1 $tudy 1£ equ\l.ibtim oona1tant• -• availabl•~ 'lhe ti.rat to e~rcy o~t an i!l'\$stlgattfn of thlt natQ1'e wre l!t.va and Ha;ebmllth(t,)• $hey d,(11:tet.mln.ed tb equtUl>riwn con:rt$.lltf tor hy~o4-.tbonf ot the PfU"~i~ :s.e riee- thtougn hoMJ'IO tor :a crude 8il•nature.1 gs.:s lll1:xtwtfJ a-t temp,,r e.tuw• tNni ~•,~ to 20f)°F. and _a t p:ressUJ"ea- .tn,m e.tmespherlc, ~ · al/JGV. SQOt pQv.nd;e !)!lt .. ca•r• lnob; hy teun.d ~ t the val'.W.l8 (>f lt deC't•a~~a. fo,t au com.pc,nenta but ~tnvie, a.a ~h~ ,r~•s$lU'\l • • 1~ «re~.sed to e.b«lt :ElQ.Q £10undt am th•n rQ.;Se e;g~ aliJ the Jtf9$$~ :~• fu,.ther 1ncte.$~d.. ni. •quUibrtum oon:ete.nt tor m•that1e tl~orea,.4 ®.ntinU$U;{ .at pf&lltv• ~e.reaaed* tU.n® tbe't1 lloom,er and af,eOQiate:,; h.1,ve P'..t'bli-.hed a . ijU'i♦a ~, pape,r e on tho solu'Qillt-1 ot metM.ne eontatn1~ about Qf~ nltna.-,n in va.noua ~"tat'txntt (f,,Siil.tlO). 'lbe w.lute tor •t~U.lbr:tum. conata:nts f:mtl;)t.te.d t:P- thoit"· •rk ~T~ in ree..s enable e.gre~nt wt~. the· ~luet detetmirul4 by «-.ta :a.nd ~obm~th ( 4) ln the lA•r pr~.S$U~ re[.l;ions,., .·~ t~ the .lowr i)t°4 tic&l pre Hu.n,a · ot the t .y a~ ijt\\dl•d by Boomer and ~QltlWS, th<t ~luces ot Sqoznot-••· eq.Uilibr1"1t'A ~niit~~ppi"Qat,h untt, ~t e. 1r,wet-- ;11e.e$UN 1hJ put'ppae of the p~EH,ent wort -.s to a.dd to the: meage:r data .. ..., on ,qu111bt'iwn qouste.nt• l>y .fl syete:mattc $t~, of the fol.l0wt.ng •rstem$~ ' • • I 1) The metil~,entfUle Gf$Wlll.J &) The utbo.~pl"O~•pelltane ~yPUnit; ih!it f~ll~ measlt,...nti, were ~Qlllpleto4; +n th~ ~eth$ill(J.•pta,n~ •~tom date. Wtli"e obtained at 100°1,.., lt\G~F~ , 2aot,. ttem a.t.m.oaphe,~ ie preseure to 2600 JQunclS, ~, •1uare ineh., tn the me-bhn.n e•propane•pontane a.ystem.1 • . pl'Qpalle to pen. .. re.tiQa •re studi•d with n ~ proportions of ~thane at 100.~F. and 300.• 5001 1000, l&QOi! 2000 pounds peJt ll'H¼~ff. inch• -~ i~li~i,WJ,,~•~ ~ ef~l'a'tue ua~d to Obilain the e·4Uililtt.• sau1pl♦~ ~t gat· and 1$.guid ~O:nfll&.s•d £~r·n of the eq;u1librtum· eGl.1 ¾,_ $hewn in. ,t~~ l,; SCl1~ua., ~ high pn>swr• $1JUrca ot IDA11'euty J; ~ira., a ia;& inj$·<,;tl~n ch amber .! I ru:!d ftm\ll,y~ a pJ'IUS~E.t baltUlC$ a·conn.Qte« to the equ#.lk· bl'i\ml eell th rough a plfes$\U"• t~p .SJ, !1$fet~ to the fig~• the equil.ib~um ~11, •o,$l'J ~btf>n't . ' ' •, " -~ a.pl7:)~;ld.mato).y l U,ter, ·1~s ''Jqutppe~ With .t;i. .s·tt.:rt1:tt- 1'ilbteh wai intJ"¢ d-UQl1).d - th~ugh pae-~ ilWJ.d and sup p o ~ shaft G an.d Will Hl.~ • • neewd t;o t\w ,u.volt ll~t• and vJe.~ the, .me,touey ·:t:~"1fel. •. U$ed to fQl.low ap:ptogi:oote;~ 'lwo 2-mtl♦. :ni,e t•l wires ?.-~ ·!-·•at;»ut_ t.,,. o,ntt.,. meteli'EJ l.$ng • ~ pm,d.deti to d.:d irt C'Qrltrt,Uing the poaiti.o-.n Gt the hydroear-~n liquid lowl. 'bridge et~eui.t• Th.<a wire.a were ¢0nneoted into a whc,atitont Sin® th$ te.te of hQta.t d1ssemtne.tton ft'Q~ a wift ') in thj) l.1~4 phast is greate1'/" ~mm from e. wite ~ the go.•L;pha.se:i ~ 11;1tre.duotio.n ot .a ._ll current 1n the <d.)"oult i'a.J.sea th~ ~~a-. tu:,e Qt a .ri-A1t tu a c1.:at phaa• mote than one tn t~ liq'U$.d phaa.. !l.heref<>~ ~•n tiw l4\Ui.d enffl:Opes the l•~-r wire the tom.pu•·•tve ,7 of the m.·~ \tn,pe u .tta naiirtaneo.,. . l1e3Ult:tng. in e. lle~reese , 11d.a ' )' c ~ ln · r~e,$ &~... ts. me$$Ul'ed bf the wheat&tQM brlctge. 1 - 4~-1 ».etitn of th~ l.iq~ti pbau ~Y 1ili1$ i~ane •~ ~do.quat~ ~t low of • ,~~ij~e!i'i.- wt~nQ• va;t.u'1t tn the n~iglfborhoQd ot the ort~oal n.gi~u¼ ~ . w :nu.re the.t the lf;qud leve,l. wa.s 11ut.f~1<mtl,y hlgn in th• hi~ p~sa'" region., the appro~te volume ot the _U.q,llid ·pha-•e:• «and the p~u~tt.i on o·t the mercury l•wl were used, :the p~••~re ud,,s t:ln~ t'll this ~ll - • ~-~ bf a flu-SA pt~·tJ$UN 'bal',mM· wnt~h h~d a w.otk1ng t~~ tt~ a•t,;ph•wlt ,~~,-~~re ~ - 3()Q0 pound.a pel' squate, tneh* »ie a'beQlu~ p~babif e ;tn►.r ln P"-seu~ m.¢,a~lll<fniHt -.s appl"t>~lm~te:tv 1 pound -l". •~r• bl.. · lt lf.'ae co~~-4 to the -ee_ll th~ugh thli> fllq.d ~t\liSau,e 'fJl"e.p !,, A eorrect:ton was ~(.\d~d to tfu:> ba.lanu r~e:,ding tt aQ.e0,;W1t :ttr. baromttx·i,e pr~esure '- e.nii ·th♦. mtt•¢nty e.na. ~ll 11be-&d1n ~ 1he teinpe.i-"!!l.t\ll'e of the e~li was mainta,ined: at ll a :e i.~ cC>nst~t vs.lu.e by ♦~:ri!ng it i .n an ail ~ :th, fff,(lid.pped. with a ~ r ~. n,gu.l1l.tor u$ed in efinjunet$.()n.. ¥Ii.th ~ Sltl!tll he:$ .~i', ~ inai n~in te:"4}il$tawre the ~ ~lp o-b ~ tollow!ng ar~♦lii)tnt w.e ~~tl, ·~· . A. e.pp~t • r Ct>.:ll, thr<>UfYl whi~ ettlam .e r (>Q ld wat er eGuld be ~seed.;, w~a ~re~~ i n th~ ezi~ TP."..s waa llrovided in o,rdRl.r to taoilite:tc, Tapid he:atb.g. ot t~. bf!l.t h. ·1wo exterio-i- :nes.teri ct l.-600 411d OOQ watts :r.esp(tetlvel:, ~~ ~•~4-: 'Th~ bath wa:s ins~ated by on• ineh ot $·&% magntfU.~ . Th«i two h~.e.~rs ®Uld 'be 00.~ cwd 1n S.tlt'i(le 0:t J~ patal,lial; or ~a.oh- , ~uld ~ - t:>pt,,t~ttd "one (;}f' in qon,;)'t.¢1.e~~n w:$.th int~rne.l re:stJSte.nt•t ~ - <;>bt,;l.~ the <l~st:red exuu~~ 1.nput,. '.lbe '7nl'i,eti♦n 0£ tem~ra~ V4,tlh tw f()X' \lldtb ~fl:iti()Jl tn,; t1'e cell WS.$ m,t &Ul' 0.,1~,. P~-esu~e ~r 'VQl'U!Ile t)~eJ viith:i.n tbe ~rtttJn of t-Jle eell oc~\1.p.$,e4 bu ~ $ M~P~ 1Ye·re Ql'Jte.ined by injecti,,ng ~r wt:tih~Tft"fJing ~.rev.ff taro:• a 3/J.f lneh atee1 tu.bit p$&:sing into the bot~m i/)t th~ e~J.l. ~I ~4 U~i4 e~pl•• £or analya18 WeN r~il~rved thre,t~li 1,/6 inch ste~l U.:it,ff. ,o\11B._~µ~ •i. . (Ftgu,-• 1) NfJ;l${;-tt~lY~- wM..ch led _to the .. EF N u B M L D J Li,auti pent~ wa~ }?Oure,d into the equilibri~ ®1.l direnl:V~ ~en, a.rte, the top o'i' the eell. was replaced, a · im.<..-uUIA i;n.1mp rem0',-ti4 wnts.ne. va.:po.l' tor a Shan time ts ~ p out all tra.eQ.$ ot ~~. , Jf♦:Xt p;n;,paue or methane 'Wa$ :a dded by the µee Qt the ge.s. inj1$.¢tion che,m~ .! , ahe material was e.Ua~ to -e nwr lt from $'tore.{%e oylinckt' Ji_ l}y wt~ dravni.~ ~l"~Y t • ~e bo·M;oi~ ef ebOJl'l~t _ I , ·• th valV$$ - acCP,l\ ~ F elosed.. • After ol~$i~ val-Vl!J ..... O 1.n.e~eu.ry 'lila$ tel'oed i.n~ the · ehaw~ • • • 'Uin-til th-e p114a:su1·$ e;i,teeedocl th~t in th$ eq_uil.11>-riwn <n-ll so th~t 1/fuen 'VE/..lve. E,. 'li'il\G epened• the g4\-.s .flowed tt"1>m. ·the inj.ot1on er.amber- into the eqt4li.bt-1uia Qell~ :lhe polfition of the nv,:Il"eUt'y in the in:ject1o.n ellw:rim;r We.$· fol1<tr;e4 by eon~<Jte ~• ! a.nd ! ,which ""8:N ~0nll(l4ted tQ 6 volt lighta,* ~it; Jtt'()oe~s ,;;a.s repeated ,un.ti._l the deai~ quantity tt 1'le ail bath W$.S ne~t brought up t() t~n.p e~tu.re. .111, ~m.poi"a- ture aiaij mea·$Ute.d by a •oppor~nstaxl.tM tMrmooouple f.w:itn••~d in the oil1 the thin:ttiie4ol.i-ple waa oallbrated by oe..ap~rlson With • &et oe Buree:u ot Stt-w.dar4s tne~'t$.%'$• •Attet e.d.Justir~ ·tht liquid; l~vel tc> the desi~4 po$iti&n1c t-he· s,a.-:npl~ was st:i.r'Nd unt.11 equll1blium wae J'~~ohed.1 as a,oe.r ta.~d by o-onste.ney -of p,eGs~. Lu. · the t}):~ee-.. ment ot e~uiltbri.uni the tntero$l .a gitation vm.a stop~rl ~ -the •~1.l>les withd~'l/'Jn.. Dut'1ns the rem:ioval of the a-am.plea. the pr,es$Wf) in t~ ~ll·wa~ k~pt co-n stant by -$.llowing. raeroury to di.~place ge.a and :U,qutd from the c-el4 1he gas· san1pl't ~s throttled $.ntC1> the W1alyti00.l &PP,&:r•a tus dir.~ ctly l'tQin a valw ~rse4 ·t n the qil 'bath♦, was thto·t ·bled 'by a val~ outsid• q Ute U.qlUd. oil be:th but th~ lJ,t.tui4 lit$ was £ill.et with m.ereucy befot·~ e.u.i.t ~,rt~:r the lici'IUti ~ple wts wt~~· :tne methEU'JS used oonte.i.ned 0,1 ~r eent ~r-bon dio~@,. In th~ ane.ly$if of th♦ $wapltt,,. thia P4Jr•ntq• of ciu•l».~ di~df» •s ded:ucted in the enleulat1•n of C011\:P()8itio:n_ At a lat&r Pori"Od the meth~ wa,e pas,ecl tbrou.$h e~dillDJ hy:droidA••activated o.e.t·~n, ca1eiu.m ehlori<lf ~ ato1;u•i.te to rem.Q'" ,va.'Wr and <,arba:n dto~ia.., 1b:e pen.ttitXIO conto.lned a small ~l"~entage of 1sopentfM.1Et, The equiptll,$nt u~ to~ th(3· {l®y&t• oil the •.i\\r.iples. .~ Otuilif~d. of, two lQW♦J)."e@s:ure • low.wmpeN,t\:l~ tr.aett.onat:i.ne;, ceiwms aa· developed l.)y Pedb.1 ~1ni.~ ~d assae1atee.·( t) • lh,f;t cql'Ulml uPd f&'t the 00 inehe$ 1~ which was enclQ$<$d 1.n a sil~i~~ -vacuum ja.<,~il., 1h13 tubir.g \'Jl\$ bo~d; slightly to teke care ot ditftrentie.l eont~a.Qt~.n o,n eooUng in the colwan.., $he only break ~ the • silve-ri~ Wti.& tor a .small inepe,ation. 'Window ne-ar the top of the ooJ.umn. Ta c,trta~ m~:i;.rnum. ~f$i:(ii.ettq in cQil,tmn operati,on :and to a.t Wn &. in~~ oap~;.tw l'lith only a small hol.d*UP Qf :U.qUid;, a flat heU.ee.l strip ~t n$clu'Grt1e was found w 'be supet'io;wo to the .etanda.rd;. pa~k$.ng& 81,J<:lb $S wire e,q1l$.1 &\U'l"Qund:i.ng thil to-:p of t.l:ie o.olu.mn"' lhi~ 0.li.ambea, was :an e:J!lten.$iO'A • tUld enlargt.mont of the v-&CUW\ .jacket fi1l~d. with :fine eoppe1r tl.inli~$ w p>toxnote h~e.t tnms.f.ercnce f;r.Qlll the · ao11de~~.r~ 1b.e cllembe~ w~a ~leo equippe,d with fil- 50 watt. heat-er t .o f~eil,:l,.tQ.te the rapid ~ .ng. uJ tho couden~r ~t,~en the rithdre:,'JEl:1 ot tv.ll dt.tt'ere.n t ecmJ?Qnent~. ihe top of the col~ was cnlari;e'd a."ld O:lti@.d with a. gt-oWl~•s1a.es ~topper., ~ssinij ~qgh the groun(l.....gla.C$$ just at the toJi;:,t tll~ OQ;tumn was a 1$e.aled i,;lo.,$e t--ube of $l18.ll di.wneteir wh:i;eh, ex~nded. just b(,).Q\'f th@ co:nd-enser-,. ~ tempe~t\1.i-e of the re.fi~ng liquM waa aeo.ertt\i®d by ple.oin& .t l tllQ~~rttiLple in this 45la1iHi t~ui••· 'l:h~ eoluam ue:ea for U,1auid samp;t.f) ~l.y::,is differ~d b,om ~ ottw:x· eoltll!Ul in ~iff (the li1uid ~elUtnn ~ing; \1. 5$ in® lf#~th ot ti n.c i. py:rez tubing) tmd in -~ uee· i;,:f ~ un~ilve.:reci ~trip el.ox-~ ~ . whole le1~th 01~ the coluinn .for a w:lndow:. ln w~,r to #&-¢ili~:to the u1.ainte~ee ,o f tie:Cl~ thNU&lQ~t the wta.l l<Jngth ot thii) oolumJ:1~ tlie eolur,ll,,t kettle$ V8're oonneeted to tile i»tti;nn of th~ -.~um j'a~ket. di~etlt ffJf t.b.e UGe •GI ~ · i'i.ng seal., a part of t.he kettle 'bei~ plaae.d in t.½e l,o~r ptU't et the ve.ooum je.~ket11, 'lhe ~ttleti were e-4uip:Pf'd With a oomplc inlet near the top and. with (i. eap.illacy tuw e..t t:lie bottoui, ·which se~d ~$ ~ .n\Qe.ns et el~~ing the, kettle and. whi® would p-Ji'Q:,nt\e, :a li1B®$. oi FQL'lOV6.l Qf reGidual nydroc(U?'bt;>nS ,in tb.e ~l.6.ly$t:S 0£ more eom}.J'le~ m1~u.ree than a.re CO:n$idered t:n tht.e tbesta.~ Selllpl.e,s '"'r'e thrcrbt:le.d fJ"Om the eq.uil.Jbr.ium cell into the enQ.l,ytiee.1 e.ppa:ratut a.e desci·ibed .e.bQve.. Jl..fte:r patdnt; thr-oµgn • 14e~• t.re.~ 1 the $~$ was ~ll~d to ill.ow th1'.Gugh tu~fll ot W);gJ1•llum pe~~hlo:r&.te to re,uw:i,e 1noitture e.nd then into the eo1unm1 llpo- dll!I""· 'ttllAtion. the s\,paratetl g~s •c:On$titU..lilts \\'8.11'$ oolltlete.lll 'i n ~ ()tw· o.t e. set of three ro0ei~ tli$kf, ha'\l'ing eapaait;t.es 0£ 2®0, 500 ~ ZOO millilitEJr·i;_. F~s~otiiiely, • ilhese • receiving ila$k$ • ~ pl&ce(l in i water batht iim, tempt)T9,~re ot "'110!1 ft$ maintatned. a~ fl 0011$t$.tl.~ n\lua by the us$ e f ~ 111$r®ry · r4'gulator $11d ' rel-y $ y e t •:• · •Me;~~~ man<,lmetera were us~d to -mea$ure t.he pr,e;aiW'ee in th~ ' C$.libre.ted ' •. reQ,e,i,v ing; fle.$ks. and -to me6'.1;n.w~ th~ pNea.u re ill ~ di.$t1l.3 .attQ • All p~·t& o:f the appa~wa inoluding 'blle ®lU!?U,:t j~~kets ~re eonnf,H.l'ce.d tQ· a vae~um he~~. $1:e vaeua war~ \'ihen obtain~ii by a -~~uey '11'ap()l" pump in "ri~e 'With Hyvae PWilP• ~l.~~1'.~1..9P, •t te~~..Aua~;:,~ 1.be, volume et a c~libration flf4.tk ot ~ t , 500 ml .. eape.,eity was determtnee by Qighing it ~pty and. filled with vmt,u·. It•~ then se·a.led. w tho dJ,$trlbutie-n headet, :flow ~ allowing .~s to from .·t.he ~a.U,b:~ated tlaelt into variouo pe..na of tn. e.ppcu-&tU31 and noting t~ ec,,n$eq\lQnt pressure ehe.nges e.P4 the temperft:t~•> the volu.Qei ot tb.e eo-l~., the oolltcttng fla.ake and 'tihe oonneet.tng tu.bing ~re g(i.l®lat~d on the at$\lmpt1on ot ~rt♦ot ~• be.he:vtQ~1 'lhe ~imum. d$fi 'e:renoe in a~ c:>M ~ueh measurement fl'Olll the rne:N'l W$S ouly about ()_,5.'}6. Wi.~ the uu ot i'Qur to 1~ mee..$ ~ment$ .t'h4, wluines we:re e.seei'tab:led with a r~&$0XU1ble de$ree Q:t tleoure<zy, OR,8re.'4~!1 °~.;F~a<'t¥!!t,!:M f.Ut;~~™', At'ter ar1equato &vao:ue.tion of tne ool'W!Ul jQ.oi.t, as well &$ al.l m;iee13sa.r:y pa.r t.a oil the apparatue. tM ~ampl~ ns lntrodu"i 1nto the. et:11.una:i. kettle,~ 1be i~S~· ~re eond.$ns~a 1n the. ke'ttJ.e. br the 1ril. e..nd a 1n,i1~lmtµa of :60 mi. of oo:nden~ed ge.-$s W"'-'l"e u;ted. Stn&_l:l.,lJ' atwr:ple-$ than 10 ml, :red,u<:ecl. the Mow:·ac.,y Q.f the a11~:L.ytl~. 1.Arge'if.• t1w:.ples than 50 h•l.- were in~nvem.ent._ '.!he top i;),£ the CGlW~ ft$ then tlO&l.e4 with liquid .~ir tQ the re.flta tempe,i·ature ot the most volatile o~tit~ent~ '.l'he ltqut•• fi~d sa;mple was boiled by lo,vedng the U.quid a;tr away fTQm the kettle t;;,>t,1 ~ "l.h~ ee.so: Q~ 'li>utan<l-, ~n~ a.mi high~¥' hydi~oca.f'b¢J:n.s.;. by he.e.t~g it with e. small (;t1Kter-i0,r el,C:l«t:ri~al .heat.et. :tt. was tQ\UlA. I that the ~st di&tilla.t.t:Qi1. re:$ults 00 -. .. ld be obt~1i1.frd, bf the ptape.r mEW.ipulati.on in s.ppl.ying ~nergy to the ~'ttlll; eoeling the top:• and Wi.thd:na.tdng ga$• to ke,e J t.l'le te.fl~ j~t Wli)tti:r:~ the J?llCki.ng the. ont1M le.n&th <r,f the• eolumn 8lli &iviug a 4.t"Qp t8'~ cit one drelP ea.eh l•·lO .&e<,\::Qni:lSs., T".ne QOlumA wa~ 9~re.~d at 1 atmo$phe~ in di$tilla.tiens (4,P th~~.~ pr:G,~ but a press~ ot S~ ~ . of ta~rcuey was UR(l at r:thieh a. ~ t Qt two eomp;>nen~ 1,:G r.e~vod instead. o-f o~:,, The ~proaeh t o t...'le ~wt was j,ndl,c-~:t~d 0¥ ~ tena.e.n-oy for a. deC~!{,~•l;le in the i;;olu.-nn. pre~nure and in 't he re.fl~ tempQ.r e:ture $..~ deteete.:d bf the. ll~~f in the elee~.omotive £QT® ot the the.r,.oocpupl~ li-13 r1~~i1ur~a, ty {.?. pQt '31:1.ti.~ter, fx·om the liqu,:i.d, ffbt)n th~1Se si£91S. appear-~d the rate of ia•i re"" lhe l~st ot the gfJ.S is re1!lOvJ4 very .al.-owl,y111 • metha~•pcnt~ne rni~es this t,'B.s d~nP.i b;y a setieG. o:£ separa:t-. ~1th the m.ethe,rt~••r,ro.pe.ne, etit, a continuous, slow wit.hdre.\1&l t ~ fQ:un~ mofft e,clvantageoua. The eol.'.leoting £-le.Sk p:ressu1"e at th~ out point wa-s ~ystem !lr'G given in Table I ru:iii It~ graphically depicted 1.n Flsu~ 2, . The li~ui;tl{ · 6~~~:,,li;tien d~t a, of Fi &ure . 2 we-re detemin4',d l;zy· S.agtt_ 'e) WE,hstet' aind tJid~Y,\ •,. In "' study or n.gµre: e s~v.e~l fSQtUl'$S ·~y, .At ~w l?1.'(!SS~s the rel~tiW. <g,uantity ot: pe:nte.ne ~ ·l;.h~ g~ phase ia J.o.rg~,. b,u.t dec;ra.~es fflpi~ly Vi1,th ttn incre$se b p~as'UNi• lJovre,ro.r ~ a lll~x$mum in the methane t:ontent oeeuWs at -~ preS$Ul.'t>: ~ tween 1000 a.:nd 1500 pounda . .per sqtia:te inch~, A tux-th.er incr~$1.~ . -. - 2500 z ◊ SACE, WEBSTER 0 AUTHORS' 2000 0 (/) a: w Q. 15 00 cri _J w a: :::, 1000 (/) (/) w a: Q. 500 20 40 MOLE PER 80 60 CENT METHANE po-int .liqw.4 tmii de.VI point &e.a fot th~ methene..pent~ 0 ~;retem at lOO~t~·'- l«)~t, and ~G F:., ture., lm<lef" tsob$.'rio eo.ntlitiQ:ns tu'l 5-ncJl'<le.H in wmpen.tUN res111ta .i;n a ie.rg.a inCl'tle.ae b. tc~ pente.ne t)Q;p.t.n,t ot the g~G ~"•· ln the l1quid p,na• the l'Atfthe.no ennt.e.z,.t tne~~e nf)~:tly ''.U,ne:afl.f with ine,:-ee.se ~ . ir•asute et ®3.lt:lt~t t,$;,ett.\.tute U.p to a f;)te!lUNte ot 1®0 poundl ~r -,~?'$ lnob. , ~ 1500 ·p o~• · Pfll' s:quare tneh ti) tb.Q. el'l tiea,l pN1JSUto th$l"ft is a ff.ntb\U.t.llf •:to r•pld in:O:Ha• in the methan• .-ntent.. ·n tsult, b lno.nasing the ~mpet&w"· •&. deGr••ee .i n th~ :aeth~ content, of the. liq\dd ph~" <JV$l' the major p<>rtton of tho pr♦$SUl'O .ra,nge.,, ~ar the (e:)"it.11•11 hoW$ve.r, a 4•i>reae ~ tein;pera~ roilul:t, ln a die.e-rea" t.n t:n. 111e~•· content ot the liqutd pha•,. Qt mo,t e importance industrially a.~ the da'ta '>n the g~ ltquid eg;ut.lil)tl,uin c,onst$nt. K. $re Smoothed valuea ot the• ®nste.nta pre,f1u1t9.<\ tn a part ot \fall>lfit I.I. A graphlctll pN.-.nt,;.ti'fhl ot th$ YM"iatita c,f ·t he •~lib~t• eonstanta una..~ titn$ lld,tb ii~b$t1r"t if $'lQ:Wn. in , t ~ 4i. :l.$0:th~ noel eff-41., :\he t,qµilib~ium. c:onfte.nt to:r- 1~tlmnt.t . - a . oontl:nual dee.voe.• • .s ~ . :pre ssur, j;noieau•, 'With $. mo• ra».t d de-cna• e.s ~~ ciri tio~1 pre,$~ is a:,pN.a ••4• Wti~ ~ 1n the val~$ of B; tor ~nt~ thovv$ el~a.J<ly tb.e r-e~a of retrograa. conde~ti1>n. ,,.. a~,nding t~ •li>Qut 70$ poun4a per ·1 qiia;re inch \to the eti.tto•l pr~seve• lt l'S .i nter~uiting to •n ttf th~ reltltiv-ely s:inall change u th, pr~uniuto. oorreapo-nd$ng to the mi,ni.m.um of 1 with •O.hfU1$• u. the tempera.~. la ord.et to obtain eonilatent valuei, the e~iJ$r~nt.-.1 dat• 'We:J'e interpolated tntt>ugh the u• ot • plE>t or , .q1,1:l,Ubrt._ c,onatantt against press_.._ 1-be QmtitOtldng •s ffllpp:l~mente.4 by l&rgc.t o.o.i, plQt# o·r tb.0 FodU:et of' the p~ssu:te ~d e.1-qUibtium. o;,i,nstM'b.$ wt-au.a tb• Jteifl.WEJ J: and a la:r~,e l;l4al♦ plQ:b ll$mila.r 'ta f:t.gt.trt 2 to-r t,h.$ oritioe..l rang•• ~the, smo<tthln:g we..i.; ao-complisbtd 'bta •peratu.-e o.o:rN)lati♦.n. lbe - ..o-t.h ftl1UI& 0:t K •& o'btai~d bf 'the au-tbl:)t - ·~e then. coxnp~d 'wt.th ·04Utl!b1"iuni conatants tr• tn~rpola~ data of hous7 wt. e1t' l ~n a -tb--♦.i$n"tane s:r•~ eontun.ing emall ffi.t eente;~t of ntt:rogltn,.. and With a8:llll· oQruposiw valuo$ eoinglUt.d by Stt.gt·• lllolce ~ t,a:oey h'om de.ta tt>r a number ot binaTy $YEJWlnl-, \Ihle wo-...ti~n .l t preHnte)d in ';fa'bl• ,t:U and a re_pre!ii.fan•ca'li!'v:t oum sho"1.n in rt~ 5 ~r J?E!nt&ne tqu:Ui b:ritUil con$t,rmta at l®*.F, 1he t\t1;$bQd Uno eurve lt:ll':,elle4 tt ~tnelo.tto.ntt preSf>nta 1:'b• e:tiovt.J mentigne.d CO:nJl?Q·&:l.tf> value.a. The $.~reE»!\\iEllnt J»tuea the ~lJu& 4at«t is good.+ '.l,he -o urw t;rom the ·.a u'thorlu m1rk 1n the M.~· pre-saure J'f~if>-n ts d1'$ tQ the faQt that these Vllluee wr• baff4 11i8lnl.v on Ke.t, and Hachiau'th ( 4 ) nieecsur~~tl for a. ®mpl.o~ -,itij,m of byd~<mti»ll'J, ~• iner-e ln the ol"itie.al pTe•~ure i:>f their q•to$ a,$ e Qnn$tuen• ot; the pre~~~ of heavier ~pant:a i1101~~HtffaJ the pN-t:lSUN it whteh the eq,uil.i bt:t• •nGt~t 1,.\pptbatl\et unltfl 0f the At tha o~ittoe;l ,~w,., eiffl!t th♦ )ilt'tPJ:rttf,~. liqu!.d. and gas ph&.$0$ be-- con·t$~UIIJlY tdtnt14al., the tqup lt~rium eone~t 1e e4,11...1 'tlQ unity• The specU'ie V-Qlume s ot bubble point· Uquid f0,:r VO';eyln.g . . . A..i.1 ri,r.t • __ (S) , eompoe4,~ q.."¥ •re ,~wn <!ti.. ;&;JJ.~ ,. t va...... ,..;t ,pee~it..t...,e ~...,~ a·'. ~u• p~t,s:ur•• ®a. C$mpor:,J;ti~n • ~ kn~ With thee• data and a k.ru>wl.adge of the I ------ 0.8 0 ~ --- I I ,_ I BOOMER ET AL, CO RRELATION AUTHORS I f- I I I . z <( ' f- 1/ <f) z 0 .60 0 u ::i: :::> ir 0.40 OJ :::i :::> a w 0.20 \,, ------- -----~ ~ t::c---'""" / / I ~- - ------/ ~Pfltfl$ t;iont r.,f . the· Wltb1~ •~int l'\l\~id and dew ptt$.nt $flt.# . ~~ .. f~•if~e v-ol.~$ ~, the ~w p(t).nii g&·$ •r~. ~•tetmt~d: aa • ~othn tf ~m~t1tt~r11, ~•se .4-a~ $.1"-e ~. ,.~ tn ~~l~ I ·.~ ,r•imt~1lf ptetu.~<t f.♦t itbe 1eo•1. !s~th~,r.m in .1 4.~N ~, lbe ~$>~e tn th~• ttl)Qeific ~;J.~ $f b®ple Jf)int llqut.d wtth ~ehq~ ~ • t ~ QO:>;it~nt ts ~e.l.l« , Xht) l ~ r por1lioa at tbs ceul"tt$ ULttlt,e;e~ut :t;h;tll •rdtnate • s at a pob.t &I . ' el)~.re$po.~du>g t0 ~h~ •pe·.IUl!.o vt''.turAe , / P,U-l"Q liquid ,peutaffll)• • '.!he UpliJ$r per:tlon ot th~ eu~ e~ ~t . t.,p1<1 L"'l,~ff· ·~ ~peeit:i.o 1til1b.u1:1~$ tltf .dew point $.aa. ft~ e~etrlii.~n ot. the 4e"r pobt eµ~ would :tn•r•ct tb• qrd~te f4t a ~ ,~ t qt:):l'teia~ndi..~ to the t.l~l;ifi() V()l.,~ t.)f pure satut-•t«ill penii• The e~pertmen•l f'!JGUlti relat-ln(¾i to the meth.$.ne.ptopm:,.e• ~t~ a.e:r1fJt,; ~re ~ffn 1n W$bl• IV:-, b ~•1;1i.tu.,.n: ot ~~~1s:tin$ pna~,· Qi~ p10'tte4 on etn.ste.nt ~pt:r.-a,~,._ ~ t u t pnta••" p~I· ·tn rit;U$4 e, ·uo );;G i.nollll.ft'V'fl., roquiliet-1• etnttant1 ea;teuia~4 f ~ tll.e ~omposition dtttt\ $.Te ft!.llio p~$♦nw4. ~ !(l.l}~ l'f.11 ln Ll~~ t, .$ " ~ tht ~ta ~~~--~ the u:utn."nttl1'•~" Ngitm_,. adiv~tiD •e t~n qf the. tf.mflielty 9.>t 'th~ . 11\Uld ~-t.~ tl<>n ¢utve,. wt th the ~-~pol-.tot u.,~4 ~mpoattaon eutw ~ Vtt,q,~$ r.,f lt l;lJ • #Wtction, of th-$ mo,J;e t~ac·U on tt' pr~JQ.• ·.• .in ~ . u.,uti ~a,~e.- th.t $$ii phf,1,•$ f#t:$ ~poeiti.oa ~~d • t,e.leu1t.tfJ4-, in tb.~ h:$.ghit.f ' presea,tte . ~g,t ( .~iOQ Md ~OOI ~;/t,n~,s pitT •t•n bob.) 'Wh~r~ -~ erttie«\l ~c.m~sittoa t• t.n tn• th.f'4:e cQmpo.n~nt .r i•tst•~ th& eurv-el ·m ight be· ~xwndeA 0t1 the stmp~ pqft\l.lt\t¢ that ' ' • . . tht n1.0i11t ~ • ' ' ,. 0.6 "'...J a: 0,5 w a. ._>-' 0.4 ::i <J w ::; :, 0.3 ...J 0 > <J ._ 0.2 u w a. <I) 0.1 10 Fig.- a. 20 30 40 50 60 Ef'f4H)t ot ~.$ght p&JI' "nt • ~ on th♦ •,,.•~• w;t-. ot bubble po.int ltquJ.d f!Wd d~w ~bt •gea ff/J.# ~ mttth~•r.n t~• tytwm at l~1:1Ft - ()t the. p~,a~~ It w-&$ i,,n ttii, manner th.e.t tlle two c;:1-...r.s•nt ·J?Qintq, ~W1l in FiguncQ $ e.nd 10 Wl)te ·- ailul.€1.t~(i,, Suq . ~-- po.int$ did ®t app~ar eQ:n~l.$tent with th.e- e•r~nte.1 ¢~~•,. th♦f -!,'e nl),t -u:till•• A ~melt GD. the !.nt~u·~lattA 90.ut$ tot- th♦ e·a1J phe.S$ and: tlt~ $n»Oth$4 lt val~, ts (;.fford.1t4 by tbe- tt\~t t.11$.t wt<m the ~l~1 ot $ -tor tb~ tht'!• C<t•n(lnt••· t~ molo fn.~tt• el ef.l.~. «lropQll(ilnt i.n the Pl pbq• ~ " iital~\3le.•4i llh•· $Ult ~f: tht_, t~ctipru1 must W; ce-~ l. ·cer> unity~ - ~~ - !.nterpolllt•4 v•l•e. 1/G--r ®.existent :gh~s&· oampei\1:tlom •d •tl4l11Wim «n:u1tant.• a-r ~ $iiti:e:n tn t~bl~ vi ttg-u,re.a ti t;o lt U4$.eat.o that ecxce;p t ~,- a slight. -.-.-.1. flit low pro~~ntG• tat,iot th~ liq~« Q.OmpQ81.tlon line, be~ t•o .po1Xnds pe~ Jq~n ~~ll g~e ne,s.rey st.~1$lrb, 'thfll me-~ in o~<H' \$r.d1, ooneentn;tion bl th•• liquid. J?h$.8$ ·'V'tlti."• ne~t, dil"ll~t4' as :tii~ .~ti~prme ¢entent 9f the lf.<1-w.li phnfilJ♦ At t.he •1~1". prell,$U~~ • 120'()' aj.t<1 ·5 00 ,...--A4 nAT snuaN . #.neh). th• •thQQ toute,n t :qf, ,~~ ,p-..,.. ' '• ~ t,b(f ' 'ttquj.d d.aon,ase.s with ino.r~..~ £3,i p'rP.pe.nb (l(>ntent:• ffllile· at: ,~.,«~• •~'V9 •'l»ut ·?OO ~~tl ·pii>:ti ~qus.1'$ 4.:aell• the· ~ -l'iJ ~~¢t1ott ot • ~ 1n~1ttase.Ci wltn 1nc~,-s~ ln ptopne. 1'ont$~, tn the ~a$ ph:Q.$S 1 e•~•te.ll~ at th• J:owor p~tieute:i ,- tho J?$nt.~ fraction un4f..r,g~,, -.~ ox- lt•• raptt eh~es. ~t '.both ~., a.nil high prQ~ ti'aeti.11n1, • At the #..nte-~ 4tat$ pre>~ t~,~ion,, t,.l.te Pf)!¼tane oonte~t of twe (sflB i:~ ~'""'iY «?nettmt-, With the ~e~~le.t-~ ot m,r.EJ ~~per:im,ntf,u, 4nt:$.1 ~bly 'fol' th~ hi~~r prope~"'_pentn.no t'$tlos, the D»t'U- •~ot natu,e Qt c.oml)t'ai~ ~•n trends ma.,y 'b~ ncte4 and $. ~r-e e.eiJu.rei'~ calf#U1$.t1o,)1 f>t equ$.U• bn~ 1:tC>n$·t ~ta mA®• ~ :- t:i;dliitio'llal ~ta wil_l .,ua·h~tp tt). ~iitablish tha ¢'d:ti~a.l+ cO):agoaitiQU#· tn4'1owt.$4 e.t 1.ffl)Q and .~ ·. ~und·$ pef aqu:are $..n@.# ~ - w,:,e ·drawn conneett~ the ~,d.-eton, oit ooe:d;siaeJ;).t ·' l.:tqta.;I.d and taa pha~es., 'lb~ ;.iiO.li.d 11ntiH> were bas~ aPf.)'.n the ~ctw1l. ttata Md the clotw4 l~e wel"e the re$uliti o'I the Qal,C)u.l~tio:na a.souo.1$d A'b<;l"ve,., :!.ite ~fe ~mptt:ititiln da:ta. .~ s 1'4:lat<#'4 t~ pt$:, sure: $.ct 140t1,. ~ proaentf;Jd. &$ a tht4'♦ ®Ptdinate plctu~ in ii~r-e 1a. fbt; ei:,ii~~ i s preiif'U.J'e'~ vmtle eomp>#it!~111s a:r~ plotted. ln oEJXUJtant. pt·Erea,ute pl6n•a. ihe intt1l'$e1)tt.o n, of the ~ · and. U,quld. c,ompllurttto,n ~JWelo:pe . with the three bQrd;~~ pl«mea oG~~pt>n~~ t() ifm•· "two!ii!•· COli'l;pc>p,ent $yswmt giVQ the pross.u,;re,;,-O'Om~attion ·41$ii'~ .fo:r t n•:s~ t;,yat¢m$. In ·th.,j twt1 · - ~ i Qf bf.n&:ey iy~• involv~ wttb~, · th♦ ~,;wo.pna$e ro€:io.n» a" $n&®4 wnere•s tn the :PT<'>~tiil!)t}nt.~ •ay:item • ~ · dot.ted lbe.$ e%W.ndillg .t~ni l.~O to •42 pe'3U4e per .Sj\Mll'O :tnllh •e..:r ~~·. l'lot'tQm of ·the die.&~ .a~" \itecd t'4• ~ieate tb~ Ji1$tit4i'Jn t>t the two•pha~ 1•egi1n, S<>l.id 'lUWI a:r• ~vm :ro1t ge.s e.Qm"intUJll ~ · d~tted' •line$ for llqutd eompe$i,t'i on1 e.v p~e•su~• ·o f 190, ~1000, 1000,. iooo po.m>.41 •~ ' sq,~r.e •·~ Ill iaddttiQn the i•oue ot ~ll bldt~a~a- .l?l~ts ~f .eqJulibr!i.wa O(ffl,S'Uffllts for methane, ptop.u.e e.nd :pent$.n~ WJ'&U$ ~Jtcent ptopai-~ of: the propane, · PQ:»,.tfU;le C'()ntent ·o f th~ it.quid phe.Ge at. (}!)nat~t pr~$siwe ·a.re E:lhit~ in 11.'&g,wei 1.1.. 1;.,, ~ 13, ~~pe,etifllf.- All. ~i,atf3 sh~Wll 1Xl the~ gt~phe . betwe,>n ,f1") and l ~ are inOOJ'J?Dl~~ point$, As a cor.. seq\4ei1ee the curves ar-e dotw4 i.n this re~ion. e11:oept 1'ihere a,dditional d~ta at 10~ (metn.ane•pro.pane ~yate:m.) save mo~ ,$ ~i.d. 10 i,;8.W t.+11-e positions ~\t ·u./hioh K apprc1)aehed unity fof' the 1000 mid 2000 pounds per squui·e •inch iso'bex-.s . :!be che.ll$e ln '~he vul:qes of ~ even .undei~ eonditionl3 fiu· ftom / the critical :re;:. ;ien j,.ndi,ce:tiEI~ the roug;hneea of the appro~tiontt of Sot.iders and ~,.s~ocia.te, {l) in predi¢tl~ values ot K ae a function of p:re$su:re and tempere:l..we ~l.one., In the neighbcn.-hood 9f the erttieal r-eg;io.u the values devi~te ~s m\.\oh e.s 200 percent e:nd m9re from nerme.l per oent propane of' the pro~...pen:cane content oi' the liquid phase S'.U,m1~18.!i, Values for the equilibriUlll co:nstrnits of methane und pe;n~ wer,e experimentally determined for the 1~thru:ze..,.psntane iSysteltl at texaperatures of 100°:F; 1oo•'F•,, Md 220°F. from pres.s ure~ of ~ 1» 2500 pou..nda per square in.oh• 'Valtle$ tor 'the t,,quilibrium consta..11ts of m.et..~ne i propane and pente.ne vror<., expe:dw.,,ntu.U.y determined fo:r- th~ meth~e*propa.>te-.pe:ntu.ne. zoo +o system a t. 100°:F. for vreseures ftom"20QQ pounds per equa,re ;t.ncll,. 'lh e J?;!'."O}?:ane•pentape re.:t~9 was varied ~m iero to a.botl.t one. Inter~le.-ted pent t,.ne v,rer,:1 _inte:rpole:bed UP :to ~t propane.pente.:ne ra:'.tio of e.bottt 2.3 Got,1position. of' ooexis:ting phases were e:xpel"irr.entally de~nnined for tho rrtet han:e;.;.1,')l;lll.~ system at, 100• t 1eo0 and iitt''i'.. ever .the ent:tn lhe eompoeition of c.oe:deting phases .f or the mcthane~p.ropane• 100°F. at preaaures of 2001 500, 100(), 15001 COOO pounds per square o. qd in.oh f:or ratios of propane to pants.n.e of f:\.pproxim:e.tely O,.l t& o.7., ~de on ~ ternary hydroeaT:bon inixt1.,we~ A"'-i indication of' t.h.$ nfJ.tu~ of critical pre$sure$, temperatures pentai1e syste1ru,, • '.!he ftlU$~ of.' the t>W,-llU:.Qrium constants ~e .found t<> be t. ,GQmpl,$:,c f'ttnot$on. of temper-atuwt, pre&.$ ure ~ oompo.a:t.tu,n of t~ eystem. Th1$ 'f ie.et bJ:"i11gs to . light the need fo~ a l$.J"ge ~G'llnt ol :l!'e ~earoh t-o be eat'ried ~ut in thlt field,, it ~U.a.bl.e value& Pt e4utUbri.uni oouste..nts tor induatti.al oa.lculatio.n arti= w ~ kGo~ -. .. ...... 50.4 -·- · ... 1631 1855 2'19& 2~ 1028 -..: ..,. . .. 8096 2313 89,.65 86.44 . • - '9i" ·-· -.. 3-Q.,,35 1671 122$ 1144 .- .·. ·--- .. . : . ... o,.o 79"-,;61 8...,63 08.:31 8»-94 .... aa.02. 65;.93 6allV4 o.o ao.,01 .,.., . ?'4.86 ,a.is -'IIIIJt, ·• . .. 1761 .190.9 :2152 78.,40 ,,., ... --4Q..42 ·• • 8:2...90 ?t.,60 - -... . ve.46 5T.'10 o•.o 22.44 •·• -- ~.o lul.9 1580 1400 l!Y"~·. 921 635 241.,2 94.,0 Liquid Ge.a· Absoluw Methane Liquid Gas Methane Oom.poai t!on Mole Per Cent Pressure Lbs/s:q.in. Compotiitlon MoJ_e. .Per Cent - - .. 93.G'l 9~_,20 ~so.a 9~0G .... ""' 510 145.5 as.,4:2 - · - 199.4 4Z.2 122-4 -- - - ,s..o o•.o Gas 81.1:31 . o.o Ii..eth.~ r~:1.quid 15.. 6 Absolute. Pressure Lba/$4.~. Absolute CompQsitiou Mole> Per Cent Pressure Lbat/aq.,in. Table I. ~:iwesiti,o:o. 0£ iuphl!-' Point ~tq!!id. ·a nd n&w PQ,i nt .Gas· iI]. the Met}1tme-n-Pontane §teto!! TA'l3LE Il :PROPER! h1S OF THE CO-:UlSTING PRtaSE.S lN THE METHANE-n•PJiN~A!iE SYSTEM Teirp. Of. 100 Pressure Ooroposition Lb/ sq.1n .. Mole Pe3:" Cent Absol'tlte Meth&te Liquid Gas 400 6.39 12.75 s9.46 93.20 600 18. 7€.) soo 214-.25 1000 29. 55 94. 25 94.s6 94. 85 1250 1500 3,.45 94. 67 41._45 94. 34 1750 92.97 91.7 600 47.99 55,1 63. 7 7s.9 4.66 10,50 15~96 800 21.20 200 2000 2250 2500 160 200 400 1000 1250 1500 s5,3 75.63 s6.42 8$ .. 90 s9.7s 26.45 ~. 90.19 32.6o 90.15 s9.4o g7.9 s5 . . 6 2250 3s.45 44.5 51.4 59.1 200 2.77 400 s..20 600 800 1750 2000 220 g9.2 s1.s Specific Voltm1e Jquilibri'Unl. Qonat&nts Ou.ft./lb. Lt~id Ga.a Methane Pentane - ... l4.. oo 0.0275 0.6Sl 7.31 0.112 0.07s o.02so 0.45s o.02s5 0.343 o.o6s 0.02~9 0.270 5.04 3.91 3.21 0.0294 0 .. 0303 O.O)l5 0.207 2.66 0.081 0.162 o.1zg 2.27 0.101 1.94 0.133 1.66 0.1&5 0.292 ... - 0.0337 0.013 0.0372 o.oi1-22 -......... ... ... ....... 16.23 0.514 0.256 0 .. 0291 0.616 6.27 0.152 0.0298 o.427 0.0304 0.0310 0 .. 0316 0.0325 0.3~8 5.57 4.24 o.26~ 3.41 0.132 0.130 0.133 0.205 2.77 0.146 0.160 2 .. 33 0.126 1.97 C.17f2 0.217 0.100 1 .. ij7 0.033a 0.0363 o.0406 o.03o6 13.69 46.51 Gs.24 75.31 1000 19.24 24.67 1250 31.11 1500 1750 37.27 43.55 52.30 2000 - ... 0.071 1.42 1 .. 13 1.39 0.296 o.45 16.82 0.55 0.3>46 0.286 0.0314 o.4li-s 0.032-i 0.347 7s.67 80.19 0.0329 0 .. 284 s.33 5.50 4.09 0.0336 0.232 :;. 25 0.264 0.263 so.57 79.86 0.0347 0.179 ;;;.•:) · ,:., r·9 0.280 0.138 2.14 0.321 77.tq 0.0364 0.0390 0.107 0.392 75.06 o.0435 0.084 1.79 1.44 0.52; 1.?A'BLE lll, ~tLIBB.lU'M OO}JST~TS IN ·'mf.E METH.A.N».-n-Pl1NTANE SYSTEM Temp. P:resawe ♦J'., Lb/ sq.bl. Absolute 100 160 220 }l()O Methane Correlation !oemer 7.11 7,2S n,...J>entane Authori 7.31 6oo 4.92 4.91 ,.~ 1000 3.07 3i13 1500 2.16 2000 Boomer Correlation Authors o.o-yg 0.145 0.077 0.117 - ..,. 0.071 3.21 0.100 0.07g 0,.073 2.. 19 2.27 o~ llJ. 0.. 091 0.101 1.66 1.66 1. 66 0.347 ◊-113 25iJO 1 .. 19 1.2s 1.13 .. - o.1s5 0.152 0,514 400 7. ss 7,6S 8,27 0.216 0.168 0.152 600 5.34 5.25 5.57 o.1s3 - ..,, 0.132 1000 3.29 3.29 3.41 0.162 0.136 0.133 1500 2.23 2.26 2.33 .o.1s7 0.11+9 0.172 2000 1.63 1.. 6c:. .., 1. 67 0.299 0.174 0.296 l.1-CG .... - ... ·90"'·• '. 8.33 0.. 293 0.. 346 600 - ,,., ~.43 5.50 -- o.2s6 1000 ... 3.40 3.25 0.2QO 0.263 2.30 2. 11} 0.216 0.3~1 1!!67 1.44 0.246 0.523 1500 2000 .. ... .. -... ... ... - 63:.• 13 l.262 Liquid 0,.:004 32,.43 16;.34 4.04 52..81 0,.0765 5.1i 00.49 1$.f/l 0.400 S..V9 21.,1 o.osca . 4.14 47.81 Z.67 . 0,.411, 92.2 5L:Of 2.,97 S,.54 lS.76 0.-455 5.~ 35.00 0.1~76 o.43a £.065 1.~16 ·0.4'76 0~248 33.,..35 8,.,27 heterenee 5 00.02 21,..91 (4106$ 5'.l..77 48,.,oo Ga.a IIDd Liquid refer to the eompo•ttiona of '.f ne gas and liquid phe.se.s in mole per cent. 6-.63 0...; 631 87.,!36 10.46 4t~l.8 2.,.98 6:,..80 91 •.84 44_60 o.ov~. 6().,,M 4.23 5"'.10 '13.95 0.,009 64.,$9 O,.:llo . s.84 PeJrtar1e •• 14.90 0~648 !:l.,6.6 a.. e9 Q_.615 10.A,8 6-40 o.a1 . 9.,-00, 1. T7 . Propa:ae * K =· £qu1llbrium Cons-ta.Yrt 79,.87 K 14.4 s.n 8.2,. 3~ 7.60 00.33 0.12a ·2 ()00 poww.s per square inA~ absolute. Ge.a K . 86.-.16 45,..37 1,.90 ~.a() S-4,.45 37,..4.4 • 0.,92. ;1500 pounds per square i;mh abaolute !Jf.;()'7 . SQ.21 Methane 1000 pounds pe :r squaTe inch e.bsolu-'.;e ~ 35.9 ,67,.9 o.52$ 5.40 '19.52., t~·n Penta..,w 200 po1.Ul<l.$ per 3:qllal"e inch abaolui::o Propa.r,.:e: .;soo pounds per square inch absolu:te Liquid K 64.l. zz.1 1 •.99 Gaa Liquid K Gas 4-. s 48.,,4 51:.6 12.0 Liquid 88.0 0.549 4;.,23 13-.'73 ss•.oo 95.,V 99,..7 o;. 9a %3 0.,3 14.,3 Gae** Liquid•• • K N.otha:ne Propane• Methane.., 1 ~~a:itiop qf Cpexist5 a,t.a~s in t he . l)iathaue•.i;l"OP!:~:-n:Pentana s,ze~ l'e.ble IV l.66 55..00 91.67 94.,12 ~l.59 2.2? 29,., :54' 3,.,21 94.85 5.,,91 91 •.7 16.-5 66.58 6.,.18 14,..0 Meth:e,ne ,..185 44.94 8.,53 .101 5.,$8 58.41 5-15 ?0.48 o.01i. 0.093 a.a a4.s 13.,.42 9$.,82 0.,143 Ptmtane Ga$ 4?.a 1.,415 Ltquid o.fo. 4 za.o 14.4 24.,P - - - (ii) (3) Propane Pentane Methane- oO (3) 00,,,9 • 36,,,,,9 (5) &.,65 11.0 0..,514 5~1 eall!\'s 2,.8 1a.2 0.154 55 0,.4'11 25,.9 (3) 51.S D 36 1000 pounds ~:r ~ (l) (i) -- 31~., (l) 13..5 (5) · inQl-.1. absolute - 13.3 (8) J.;QOO pounds per aquare ineh $bsolute 61.,1. 1s•.o 4.7 2.0 (1) 22.0 ,,l)imda ~;) s ~ in(:) abfOlute 3.1 sa.s (1) &00 pounds per square inch aotolute Methane q.955 (3) . 71.. 7 75 Propane (5)' 6.2. 23 0.26 Pentane • Gas i•efers to composi tioi1. ot' the ga.s phase in mole percent liquJ..d ret\}r'l oo et.m.tposition of: the liquid phase in mo:le percent. K =- Equillbr1.um eonstmt. K s,..a (1) 0,.138 28.9 4.,0 (6) 0,.434 '1 7.32 40 (S) (1) 74.0 31..l 2.31 0.-506 fh,.l 3:IS.o 0.,102:6 3,.7 U.,8 11.,5 14.0 ••o (fi) (3) (1) G•s L1quicl lt Gas Liquid .K 9'.0 o.1sa 4~4 (5) '1.27' Pe11tane - 1.0 Liquid. 5().0 (3) 46.9 Pn>pe.:ne o.,9s9 8-6.4 90.0 Liqu.!d.is K* Gu OruJ$: (1) 45.,S 5.6 12.15 ....,_ llbthane Calculated Data ~si:t1on of Ooe•: tis~!5 pase.s J.n ~ M&tnane,,.~~Pent&M Szt;,~d·5 Table V ?~SEl'l.U'e lb$/sq.tn. 70 percent Ab~ lute l.0 peroe.rrc 200 500 :t.4-2 l4.l s.10 s.48 5.,2 i.90 2.55 :,.o l¾O 1000 1500 2.,09 2000 i. si i.sa 200 0~81 0,696 000 o.a15 0,95$ 0,509 0.951 0.0.20 ◊.401 0,dU3 0.,-.1.96 o.ai 1000 1500 2000 01 -ua 0.439 o.ao 200 0.110 500 0,07 1000 0.01 1600 0.104 0.212 2000 1.96 o.ooa o.448 0.035 o.ue o.Q7o 0,084 o.ias o,300 1,eo 1.01 o.95 ! 01'-150 o.~o o.ll9 o.,235 o.44.a ........ Table VII Pressure Lbs/sq •. tn.. Composition in mole percent Methane Absoluw 100 160 2560 24:3()ili 220 2190. Pree1sµre Lb•/sq.in, 19,3 12 ...e. 6?,0. Comp.o eition in mol• percent • • Methane : Ab$olute 195,5 159.5 115,3 166 1018 1290 100 1365 Tem.. o;• · PrE,SSUl."8 Lba/sq•.tn. 10 30 50 67 Composition in _mole percent lidethane Propane Pent;ene Absolute 100 100 • 1500 60,5 2000 11.0 Reference 5 35.o 15,0 • ? ,. Boomer, Johnson and Piercey~ C~"'l;"diqn .Jounw.l ot n ~searQh,~ J£, 319., {1936) fue ~uthet wtshtH, to e$pl"8SS his e.pp~eiation for the . ftlub~ advice 0.11:11 eriti~ifflll otfere<J. l)y DI'. :a. :a. Sage and Dr. W11 N,. Lacey throughottt th1e inveet1gatton. 'Jhe e.EJsist&n~e of Ml". Ii., M. Lavender and Mr. Hodge :l'aylor ui the aeeum.Ultttlion of date. is gratefully aoknow·l,edi!jed. Financial $uppp:rt t,rom the Standard Oil Company of Ottl1fo~ ~s a major consideration i,n ma.ki.1:ig tht..s investigation :possiblf•