The Pressure-Volume-Temperature Relations for the Methane-Decane System in the Liquid and Two-Phase Regions

Citation

Lavender, Harrison Morton, Jr. (1939) The Pressure-Volume-Temperature Relations for the Methane-Decane System in the Liquid and Two-Phase Regions. Master's thesis, California Institute of Technology. doi:10.7907/py65-zq39. https://resolver.caltech.edu/CaltechTHESIS:12032024-210703408

Abstract

No abstract.

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
American Petroleum Institute	Project 37

Record Number:

CaltechTHESIS:12032024-210703408

Persistent URL:

https://resolver.caltech.edu/CaltechTHESIS:12032024-210703408

DOI:

10.7907/py65-zq39

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No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

16893

Collection:

CaltechTHESIS

Deposited By:

Benjamin Perez

Deposited On:

11 Dec 2024 00:22

Last Modified:

11 Dec 2024 00:38

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'l!HE PRESSURE- VOW~TEMl/>tmATUn:& .RELATIONS FOR THE W£fflANJ- DE.CANE SYSTEM :IN Tml LIQ,UI.D AND TWO-PHASE lUi'OIONS Harrison M. Lavender• Jr. In Partial Fulfillruent of the Requirements for the ~re$ 01' Master of Science. Oa.li:fornia Inshtute of Technolog Pasadena, Cal U'orn1.a 1939 ln tl;J.e petrol,ewn tndv.•tey the predietion tf the beha.v1<:>:r et Jll'U.a. oU. natural gas, and the 'Various pet.r-o:le.\Ull d•i"latives b desj;:ra,'ble in the develQJ>m•t of processes to be uee4 w the indu1StJY and tn cqn~0-l, of the pres:ent JX1ethod.S ot producU.on and. refining. lleaults obta.hed VT the use of i11n:plU'1ed. tela.;ionahips such a.a the P•rl-e ct gu law a.n.d the la• of 1deal 1u>lut1on1 (1) are oft en g:reatl1 in error. HtnQe h i• d.e-1 iral>le to obtain expeJ-itaental results deacr1b1ng the b,ba.v1ox- <>t the•• bydrocatbon•" The pN>bliem ot ett.ablbhtng tht gas.liqil\d equillb:ri• ;r,elat!ont to'i' natw&J. ga•, erud,♦ <,tl., gaatl1ne, and ~the, -1\iooq,onent h14"~ An 4',pproach tt . th• solut hn . o.f tllt prl.ll>teia 1a made by th• st~ of the eq'1.i.lU.,.rt:\U\l bebartol"' of the •inli?let n,dl'0¢al''bon 1117ste!lmi \Utder conditbn• similar ~t!> those •co"Un,ered. ill. The methan•"'d.tcane s1atem here stud.:i.ri i• an ad4.tt i.o.nal meml).,, of a •tries fo:r 'i!'hieh p.. v..., rela.t ions have been eetabl1•h•4~ Proa.lUJ'ei U,· to 4500 lbs" pe:r sq, in., and temperatv·t e trom 7~1. t.o 250,r. we~• em:plc>yea.. MeaJJ-urement.s of eptcif ie volume in the l1<ru1d and two...phate regions were made and the partial vol•es for each oomponent in the liq"llid phase wer·e cal<nlla.t.td• JquU.ibri:wn cotUJtanta tor methan, at bubble potn\ were also calculated., '?he part 1a.l v<.,l,mifs and equil1 b.rt'!l1n aon,ia,u,ts were ~mp$1'ed with thc:use for dmilu 'binary systtm8 ¢Qnt11Jtlng et met.M lle · and a secfnd, pa.:raftini.~ n,·dtocarboxi. ,two types ot a.ppara.tue hav• been developed. for the r,nea$Vetutnt. of appa.ratus de,s oribed. by lo'Ollg ,(2),, ~ , and Jay (J). an!J. 01:i•:-s~t. atonea az'ld Volante (4 ).. lu.¢h as de1t,o:r;,fb•d bl v-w a,i~•t~• wn, second t;vpe is th♦ S\ilel p.... Sage. Werntitr and Lac•y (!;}}. 'D~.e latt, r ~p-.a.t'\tt --~ w-tth a fe• minor change, was 8Jll.Plqyei in th$ pl'etl!mt s,\~~ Tht advantage.a of the s$e:el, p.,.y,..T apparat11«s u coznpa.r., d wOh ~l.$.H appa,~tue 11.it 1n the f&.¢ts that a much la1:ge1' pr,uure t~e ~ be emplo,Qd a;nd a l&:rger sample permit$ more a.c~ate a,te:rml.nat~• Qt t.he. eo1~l<,eition of the •1•t ♦m.. 0n the oth.r hand the dttadvanta,gea lie in th• f.act that the eanpl• cannc>t be vi;suall,y obetrved tQ determtne tht phase boun4art•• a.a can be done with th• glase apparatus.. :turtheJ-.- the C't:Sl of la:vg• •lM11lle• ~f a val.tia.'t)le bfdto0$.r'be:n h ,._ aawl:)$.•~ Th, '1e\han• hei'• •td n• <>bta.ued, t:rf>,rn the Jutt.onwtllGw t1et4 b1 eaU.fol'nia and 8,J."1glna1b' dontau:ied 0.1 per nen.t ethane ant hta·de~ hydl-o@.l''bons and o. 3 p~ qce_nt earb<m di.~ id•• !rhe ~ t of n:it,rM-• n ud Q\h$X' non-condens$;ble ga,es e-onta.in.a wu n.'@ligibt:e, ,$.$ ind.tP\114 'bJ a careful Qo,nl:,ust,1$t.l .antAlys-119 on. trui aaropl$$. \lhe tneithu.e wa.• twthet puti:t'i.Jd. b•f'or• addition to \b;e ay$1'em b.¥ patsing tht,$~ oalc;t• chl♦rU.e. $;d\ivatJd ~,Ml. at~a.r-1tt and s1>dlwn h,dr,o:t;$.lf, at a p:res,ure ot· 400-500 lbs. Pef sq,. it1, ffh• mttha.net t.hu• prepar,ei wali' beli.ev:ed to e~:ntain l.•• than o. 2 p•r ~ent 1mp'U2'tt ha:+ . ~ ·I ' deo&llt • • pu:r~•ed as ch.t1111eall1 :p'V•e ~..de~a.n• troill the Wtnum Jt:o~ Oomparq;. lt wae :tti;'the:r pu:rified lti a hactioaa.ting e•ol'Oalll and thEm d.isU.lled into a. t\ee.l bom'b :fo:t •~pra,e. A diagram tf the pwit1.cat1on apparatus ie •hA>.wn 1n Fi~e ·l , \llht glass :t1tactio:raat1~ col'\lll$, (If)• -.s •~r(>\lnded by.'· a silvered vacuum j~e\. ( o). ArOVl.ad th-e jacket ,ra.s w◊und. a l®> watt heat,_. u.d the whole jacket waa thP. covered with s5~ magnelia. heat 1n.•v.la.~1t~• The fl$.sk. (A;). tonta.ining the d.•ca.ne t~ b• pw:"i!'ie.d:, waJ; $.\t:ft.tlieti -t • . the eol'1.mn by a ~o-µnd. glats Joint, ~!)• f·t tnewt a ~ ~igQt· ,,ai. mer~ . -was pt~e.4. into a. t't!p au,,:-0,'Wldi11g the $PJ,, ~OU.nd the t1i.b♦. •. .(D); lea.ti1ng from the to-p ot the 0.01,- a lOO ntt heater- wa.1 W$1lnd ~d. the tube was tnst1,la:;ed. wUh $§~ magnesia.. The heater on. tube, (tJ.. ,er"'"' to prevent. th• d.e~$;rl.e t'rc,m c.ondeneitJ& wit11 U 1rea¢ht,,d ·t he tE>tal eQnd.en,er. (ilh From here th• oonunsed mate:rtal d.r~p•d thrQugh drip 1n,1c,~t-t r•• (F) and (;). an.4 l"t\urne4 t.o the to:p ot the col~ to supply th• reflux. Volatile bnpuritie.s w«r·e ~ • d 9tt a.t th, Oi;p 1ndt.cato,r, (r). P.re••w• tn tht syattm wa• in41o&.~$4 ·bf· man0m$tU., (L). and th• .: rate at ,rb.t@ non. (;Qn1hnsa'blff wtl"e i.wawn ott wa.• tnU.c;ated by tht ra;t, et ta.1,l. ot tb.i m~C"U.rY lev♦l. in manomet..- (M) wn• atc,peodk (I) was c;l.os•4• v~~ head.er, Hi.vae puq,. 'Ph.• (P). waa attached t'Q a meµ-,(1'117 vapor p~ and a ¢.en:¢0 !-raps (lf) and (I') were immtl'•- b tQlid ~at-bon d.toxtt• and acetone to eondens• out n•.a v mat•:ria.1• i,n the gas p'Qlpecl oft ~ th:u.t pr()te:¢.t tho vac:uw.s 1-ornp•i. !'h-e •t~ra&• bi>iti'b "'" atta•ed at t-Af 'b.r aes bl.o.cli (It}, int<> wh1c:i'h the tube frtm the tll-ip lntlea.tQlt, (B}. wa,. !lealed. with sod.ium silicate. After :refl\1,X1I),g fo-r a • -~ f1ehn) ·Uine. tht: ltq,aJd. deCane was 4,rawn 1ntt, the evac.,uat,$4 bo1nb b1 Qpening .1.t~cQ~ (I)~ The bbm'b wa, imtne:rGtd ia a. toU.d <.;atb~n di~xide-a.cetone mi~'.U.t'~ di:u-ing th.is ti.mt:. iefl..ux wai!I ma.i,nta.1ned tn ~he e~l'W.lm during thl• period at • ~atio of aboul 4 parta ~f r ·etl-ux te l pa:rt of pl"odu~t. After i'.be ll);iddle ft'acti.on. ha.d. 'f!e.en distUle.d oveJ", th• s1H>.pcoek. (Jh •aa c;1o••d and while the contents of the 'bomb remained t'razen, it was 1tYa-cua$.ed tor a period of 20 m:t.nutes .. N T C B A t=J HEATER F0r purifying deeane th~ ep:para:lttJ.S W'liJJ operat,.,a . a.t a. pr.-,e~·i ; of a.bout .3 ... 6 nun. of tnerewy. .methan$.. The main i~wiUes. temoved were· ~~ ·. aiPcl ~ heavier hfdtoea.rbons co~ta.ineil b,y th• d.th::inte r t • ~ • The deea.ne. obtained from the p'tlritifatton c(fl.W. t001:ibi1,d a <ienaitt ot o. 7213 gr·all!S pe1" ee. at 100°F... ~t• 'ftu'ue diff.e;,s app:r«o·1abl.Y' trom tn.at ' ef o. 7li6 given by .:oe•• '<6)~ - Jt :p111HeHri a. Yiseosity of 6,59 Jntllipoise.t at 100•F. &1' t\tQinq&r'-1. wU.h l• 83 mill!• :po.tees fQ~ n-cl1t;1a.ne it•• by DO·t~Jo .u ·s evetal 1e.<>.meJ-1<t deeazies pot$$11S density values g,i-'ea.t• \)um t~at tor the pret·en• material .. it WM decid1td tha~ the tt1Ate.r1al. wa• ·a mUtw~ of tsometiQ detand ta~h-, than JUlJ;) ;~f\TUS' B!U MJl'IQ.D The a.pparatu ha$ 'been. described 'bf Sag•• Wet>s.ter and taeey {5). Hew·eve:r, it 1s desirable \o des.crtbe. it. b:ri.,et''ly again in eon.neetien :Figu.re 2 is a; ee.;."lerna.tio diag;ra.m of the appai'atu& empleyed... iteel varia.'bl-t vol'U.rne ¢•1.l, lh an inside height Qf l~ tnehes. the h~d. ~ inside diamet.- of 2 \nehes and The vol'wne of. the cell wh14h ws ec<n1pied by the sall:Iple QOilld 'bt varhd by addition or with~awal ot apaQe above the mer-<r1tt3 •~le \ifa.a determined. 1>1 the heigh\ d the ttiere'Ul7' surfa.(ll'.e.. This wa$ me.a.sur-ed by means of 4n elEtet~ical e<>nta.et, :J, mo'Ullted l!"Jn a. hollow rod. o, whleh $%.tended up thretlgh th•t m$i"c.w7. '1'he r.(;)d, c., ent.er.ed. the o.ell thr~ a pa.eking gl.an-d.~ J>, in 1;he bott~m of th.• c~ll. .ilod. O; was tl'wtaded a.n.d engaged a n:ut, r, which •~• dril'en -6- N TO PREssURt BALANC E TRAP ' ' Fig. ''' CO NTACT LEAO Diagram of the steel P-V-T equilibriurn cell. thus pessible to d&telZ'Jnine the height ~ the mer~ '>1 t~ COU;n\ff .: reading. The t~p of the cell •~• :remo1"al,lle. the teal ,r$,s mad:• ,rl..;tin a thin copper ga.•ket so that the top of the eell ¢o~ci be .removed &J'ltl rc,placed withov.t cb.angi,ng th$ vOl'Wlle ot the eell. 1.L'he cell wa.a bored and la,p•d to a true oylind~ whtse diamtttivarted by lete than Q.,0002 1.nct,., on the bo\tom ot the conta.et rod was nio'imted a plunge.r. Ji!., of tht aame d.i.ameter a.$ l"t>d, Q. 'rh~ pl~e.r movei'4 1n a QyU.nder i'Ule.d nth m~cVJ:7 and act-4 a• a ooatpensat~r so t~a:t a ~$l:ge i11 Y♦ 1'1lae Qa.'\lted by withdranl of the ¢Qntaet rod f:rQm the ctU. •~ exactly coiqumaate4 tor by 1nject.1on of inetQ\117 trt1m the ~OIJ4)et1tator, ~e cell 1'l!Ul c.s,librated at a given co'\tll• reading by f't;xncn·$ng the. ttp of the cell and weighing 1n crystal oil ~tU th& oil 1,vel ¢ta.uie vtrY elose to tl'lia top of the tell., The Ql'ytt~l sU. used •s a. mixtwe ot' eyd.rocubeus ·r ~intd. trom a. non-w~ ~ruttt. n ha.ti a. na.rri:iw boUbg point :range and exhibUe4 an averE)ge molecu1a;, •eigbt o1 abouil 340. The te>p •• then replae~ and a e'U;'ve 0£ pre&l'tU'$ ver•us eo-ut.r :reading determin~d, 'l'he a.tn0mit o:t ·a.1:r wh!Qh ·wa.s t:rappe4 tn· the to, o1 th♦ ctell •as ettimatftd t:o 'bt l or 2 oc. :at going ti> high pl"&e1we11 the air • !.o:rced into sol-uU.on 1n the Qrfttal oil. Sb1ee tbe a.mount of ab- (0, 002 g. ) waa siaall c.onp$red w1 th the amount of crystal oil (40 g! or larger) and the partial apec.Uio vol'\lme of air in cey-tlt,al oil is amall,. the effect of the dioolved a.1~ wail n$gli,gibl~. !l'he hothe:rm Gt pres'Vre ver•ua eounttn" reading waa ext.rapola:ted to ai.tmoapheric pr♦esure a~ which pressure. the epeci:Ue volmnt of the crystal oil wai know.n.+ vol-u,me of th• cell at a given merouq- heighi QS det-erruine<l. Thu ilh.e J:nowing the pitch ot the a.eouratel.7 niaehlned thr•Ad on tht roe,.. Q., 1t wat tne p~ss:tbl$ to ealcru.ate the vol'1tne. ot the cel.l a• a. 11nea.r- function ot $he ¢0Ullte:r :reading• lt ns found that the p0,tiU01>. ot tlae ~ft})!t-, •wt'~ • co'nld be d:•tierniu,.u with an ac<::uracy of bettll' th• o. 001 in®•· ?:hl• ' ,-1 ,0:rrt!ispond• to. a. volu• <,.:f Q,,.00) eu'bie inch in volmes f:r~ra ) t ,o jq, ~u,bic in~e•• the efft,ct of :prestti.re upon the ee;l1'bra~1on of th~ !nst;rv.m~\ _. dt1ermintd bf ma.inta.1ntng the 111$.'em •-tact at a. fixed helght u inea.•ured ~ an el,ctrt~al e:o;o,tac\ fa•t--•4 to $1,1 top of the,. cell $.Jl,d tt ns xiot1ll$ \bt change in co'UP.ttr- r•a.d.in.g wtyh in.QX"ea$ ♦ ill p1•1s,u.r et fo\ll\d tha\ \he ~t~ pi-·•••w-e eor;r;~eetion '1$$ leas ~han Q,951 :tu gtd.ng from attnoilpll,etic to•. $000 l'b.- pet ~q, ith at 'lili\e tilalti~ vol1.1lil, ot th• ~o ~ftot Qf tempe.ra.iwe upon t.he v~l~ cf th• C(tll, A, •<\\t taken into ~ce~t ·01· eal\'btation at d.itter-~\ teltpe;oatm-ert. • • Ul.9Jt:imu.m etto-r ln vol'Wlle 4~terroination. fo:r the saia,pl,•l;'S b bt:11.'eved. to be· less tha.n 0., 2 »~ C$11i The }>l"QS$1l1"$ '#at raea.s'Ul"ed. bf meant c,f ,. sp,ee;~ll1 d..$$i.gjled n.,td J)'te•••• balance whieh \ls,ed oil a• a ffi1>r~J.ng :t'lut&- '!he pte&t'it1.'e • t ttanStJ.i~tt<;d th1~h ~h• .X't.r-Ul'1'""0i1 ·t,r ap 1,n4ioaleil i:n' F·igwe 2t Th• tr~ ~ p:-ovidri with ~ eleeir1cal c.$ ntae; so th.a; th• •r-~•oil int•ita.c, eo\lld be UlSl.i.ntainri. a.t a ~onsteai b:ijlght,~ The bal•c.f was eq,t>.ipl)ed. with two totatin.g pl~e.-•~ Usuig ib.e. ••ll pl~.e r, preteures :from O to 6000 l.b e. p~ aq,. in~ could 0$ measw:-ed bf O..\n,., per sq. tn. •t~•• U$~ the larg~ ;plung,r, pt-~ 1••~• t"rt:>m O tQ 600 lbt, per sq. in "by o.oi lb.- pot sq .. il4- ,tepe ~.e tdd btt mllldWfd, The balance ns t4u:t.,pfild with a Ut:t!:tlg mEJ®a:ds!ll .tt,Jn,Ua.r \o that t~"t1t1d in tht bett~ grad.ea of ana.ly~hal balanc,11. ,h~ :fQ:,.ee t'rorn \he plv.ng.• rs waa tran•m1U$d tltro.u gh a aeriel ot kn:t;t~ •d+te$ to a ) . . . 'rhe 'balance b ~ were dettgned t .o p0$8f,llti a maxli®m defl.ellfn: f,)f less ~ha.n o♦. 001 inch in a ltti)gth of 14 in.ehei$. The balance was tensitive to p-ressure ch~•• of 0.05 lb. p,, sq. :hi.. at a ;pr·ettwe ◊t 30® lb•• per sq, 'Jli• l\ wae tal11>7a.\ld ~altll~t the 1'ap.o r pt•••ve .e f carbon dit>Xld• .a t 32•:r~ U$Ug a. ·i -bni:q'6\ •tm1le.r ,,o that -o f ~id.gs;nan (7). ceu-l;,cn 4ioJdd;e wat tak4m u A.t ,,.,. the vap•r p1esswe of ;05,56 lbs. per aq. in •. bi taleula.tug pr6s8'b;res ftoin the meaa.w.--.t.a mad.t. e~rtef.J\ltn. fe.x- th♦ oil aa4 m@C1ltf h&~s tn the eonn•ttng lb.et and cu,11 •• For t;he•e t•a•sn, it b beU..111etl that $he p~ea-• w• ~a.•~•m•t• mad.a. r$port:ed were ac~ate 'Wlth.in l lb. pel' ~q, in. 'JJhe 1iemp-, ra.1~e ~t' the cell. •• ma.tntained b.1 an Qil ta\h •tea oo~d. b,t eont~oUe4 b1 a the~DlOttat at a pt&d;«Jtf#ll:lhecl val-u,. Whit 'bath was he.a;ed. b1 an ~-·p.t.e.tn;al con\tn~'ou1!f:,hea.ter, a ditterent,2.$.l.. heat• ' • ' wnere the cell l)l,o;k pa.s~.a o-ut «)f the the~lllat 'bath and ~ small tnt~rrxni t.teni heater which uin,tatned. the tentp~aJ\tt'e on 1;he .oQntrtl: point. ·~ oil bath t•~f/L"at;-u,re wa, ••aaw·t4 iv a Mt:lell..er bTi~e • ciroutt v.sin.g a plating reeisfiance 'thtrmc>meta,x- tn ihe l,a:\h,.. Th• thfl'1110met.8l' was callb.rat,ed against a ~ea.u ot studi,rd• pla.tiu• resilltan¢t th.e;rmqmeter. fhe th,rtn0sta\ ciontrol tU'(}Uit ¢ontht-4 or a Mu.el.lex- smmted 'theatttQne bridge us,ing a J).1~~1 :reiliitance thermometer 1n the bath. i high •en•i'Uvt ty ga.l van1Hnete:r in the tti;l'... wit actroated _, ;phot~ eltctric relay eirc:uit •hieh oont-roll..a th• 1ntermittent heater. !he t~erti.tW e of t.h e cell was nu,a.s-¢ by mean.a c:,f a. 'i;her-111()... j couple inserted in a hole <lrilled Ul the ~ell bl(l>ek,. Th• thetmotO'Ul,)le was calibrated 1n pla.0e $Against a. Irores:u of $ta.ndardt platin• resistanco thermometer. 1\ White p0tentio.1neter waJS used h measur~ the thermc:>c&-np14' pot•ntials"' The temperature of the C$ll could be measve.d by thts met'hff. within o,oa,• 1. !eh• tepera.twe, gradients in the ~11 bath, ;,~• teas than o,·05•:,. Thus it h 'believed that th• te.mperatwe measv••t• ,Afsita.U,on \o hast• the attainment of ,quiU,bri:wfJ. ,4thin the bQm'b was supplied. by four unU'orni verti,oal rods me1112tted on a. ring and. driven by a bevel g•a.r on a shaft which ext end-,_ tbl-ough a. p~ld:ng gla.lld in, the aide of the etllt It '1d J\ldg.a, that G<!V.U.tbri• waaattain.a. whttn Oenco Ki..-a.e pump in •e,h., , fhc, d.eeane tras added \o \he e"ta~tM e&ll by !0~1::l.ng the dto&Q,~ trom the heat~ •ample bomb thro\lgb. -valve P. in the top Qf th• a.ell"' tru. amount <,·f (leoa.ne add.ed was de\ermin•d by meas,xri.ng the vol"Ume ot. the U,quid at l00°F,. atJ f\lnction of presewe and extra;pQla.t1.ng \o a.t,;noe;pb.eric pressure. Frol'II the. lcrtown den•H1 ot the decmu~, at a.\n1Qsphe;vi,e pl" essur e. the weiaht c>t dec1,ne addtd. coul.d be d,e t ern1ined. Tb.e methane •as added thTo'1gh a. aeeQnd valve (S) in the top o! tht c,:ell. Oonnected t.o the valve by a t\ttam Jaeket,d line was a. the.rrnot~atfild reservotl"• The steam ja.eketed line was a.lw~s ma.1ntaine4 a.t the ea.me steam ptesswe. J.te.th.ane •• p_,.;-4' btt the r:e•etvoi:r \mtil 1ih• )'eservoJ:r p:r,aswe wa.s higber t ~ the 4ell p.i eaailre and thea th• connecting val"lt was o,pened. allonng methane lo tl.o• f.nto th• cell+ fhe weight ot methance Mded for a. given -qb.a,nge in pt•H'\'.We 1n the r,servc&i:r wae determined. 'tiy running a calib:rati.on in which the tn!:Jthane at a given initial pressure was rtm over into the -evac-uated equi,;libri'8Dl: cell ;rhere ~ 1.$oth~rm was rv.n on th~ methane. !b.u$ the we1gllt c>t methan~ added. eottld. b·e oalC'tllated :from a knowleGtg• ~f the- p...:v -t rttla.tion• for meihane. From a knowledite of the initial and. t'inal prHtJ'UJ;"es !or eaoh addUi~n. the calU,J>atton wail cosplete. ~he retervo1:r had p:reviousl.1 been cali"btated "bY witmu--.wal int~ a th.-m... st~ted mer~ Q'Pl'$1h It is believed that eompodtion as dete-rmined bf the abeve methods of add.i tion wa.s accurate within o, ~- E.>:PElUJ;l!tAA RE§U:urs Isotherms at 70°1.; iOOOJi\, 160-F •• ~Oo)r" t antl 250°F. wft·e obta.1ned. •1th a range in pr:et111ure of O to 4,00 ro1. per sq. ith for ,even rnixtw-es of methane and deQane rang~ 1n eompQsitton troa 0 to l.5 weight pe:r cent methanJh $pec~f 1o vc>lume# were calcw.a:t•d at these tefl$)era.tur·e s fo.r the liquid region and fQ:t \he two..,.phase reglon for valuea up to a.bout :fo~ times the 'bubble p<>int spec.i f le vol'UJJle• 'l'he res'Ul ta are shown in Ta.'blt t.. The pat't 1al specit'ice vol'\lmea tor ruetha:ne and decane 1n tht liqut4 phase wer e determined. from isothvma.l plots ot spec.i f te vql;wne ver,'1• composition a.ceordJng to the method of Lewie and. Randall ($). ~, :partie,.l velumea are r'1)resente:d by the intercepts .• en the axet ot 9rdinatea., of the tangent to the specific vol1l:nle cutv• a.t any given co:inposi tion, They •ere tmoothed. a.gains1; pressure. comwst1on and tempera.t'1l"e 1;1ntil oona!stent within o.3f. a.re given in Table• II and IlI.- 'fhe $moothed: p~tta.l. volumes It 19 believed these values are acewate within 0"51 . Equilic,ti'Ull oonat.a nH w~• ca.1ctil.at$d; f.ot the methane in tht bu.'bble point liquid ()n th$ atJt'tlnlpt1C!>l;l that th~ ga.8- :plla.ile present was pu:,e m&thane. thus Jt1 • ti .. ~ · • \ • 'l'he resu,l,ta u~ shoWA in Table l ll• ·in order to aid in the viQualizaU.on ot the bl9havtot· ot th• •1•te111. seve:ral diagrams lla.ve been prepa.r.a,. Flgwe 3 s.hows the i.1cothetma.l p:ressw~volume o\'lfvee fc,r a. Jrd.;ictw• ijCl)..tatning 12,lS weight per c:ent ot methane. The 'bi.ib\l:• .p Qint ~v• ,nows a revw•~t ot sle:pe at a preu-ure Qt about ;06.o lb$. pet ilq; tn. ~hi$ ts thf poin~ ¢)f maXi~ . pres ewe a.t which two pha.s•• ean Uid f el" a syJ,tetn ot t:M.$ oompts1\ifn, :Beca:u.se of the great dit'fertnee in the snoltcnlar weight bett':T&t:nl meth~e and decane. t.ht .t 1rtticail •tale -.as noi reached tor the CQllptaUi.e>ne tn the range '>f pre,swe.s ~cl teupe:ra.t'Ul'es hel"t gi•~~ ln F ~:e 4 ue represented. 110.the:tm.,J. cu,rn.s df lro.h'ble p~tn\ ctompoi,ition "'i'Vt,us pressure,. fbe :rapid inc:reasse tn cwvatw• of ~he 1!$a,'tura.t.ed liquid lines a\ high.tr- i>rlitOure, i;J 1.x.pt~led a.$ tht ¢.r Ulca.l reg1Qn :h ap:prl)~h.$d. F ~ t 5 &hows •peaitte vol.i»ne ot the tytt.em a, a tu-nntiotl t>f Colll,Pod. t:l~n at l.60°1. F~e 6 pretentt the isothBl"al relation betwftn th• ~uilibriwn eonst,~t and Jl:"e$s~••· ~• syet•• Qbs·~ •d tl.id n.o,t :r:eat'lh tn, erU1¢al •tat•• !hit is evi4ent •~ee a.t the critt.c al poit)$ for an,' Jfate.m E;P· • :P (ar i,n othe.l' word• the equil:loti'Wli qonst.a n\ ♦4-,, one) and both Jhas•• b~ome oe:nttn.'Ueutl.1 identical. ~ was plottM :tn1te•d 0£ ! since it red.ucCJa the variatic.,n in the cruanti.tlea pl~Jed.~ The taobari.e tel~:Uon i~ the lS.q'\lf..d phaat 'betwt,:en partial ap•citic volume and. ccJllpOtitiQn for methane and for decan, ft>r a t, enpe:rat"Ur♦ of 160°:F. 1s shown ~ . J'lgwe 7~. FigWe s j,ndica.t•• the r•l.a.t ic:>.n in the liquid phase betwee:a. the partbl tpecitt.4 -vol."llnle of d.eel!!tte and pre•swe -13- tor- systems 0f eonJtant co~o,s'i tion at a. ten-,erat\Wt; ot +60<>)\1 ,~e !lf•t•m eXhfbtta a poi:ttive isethertnal eoripres,sil!lit1 in \he l/>iwl)'b1e point rtgion for th-.. higher eQmpoait1ena o'I rneth&i:c;• Q-OlUlS,~ lmtffl lt is of int erest to afi!Qer'h.in th;e offeot of cb~mical nactw, 0,f the oth~ eomponent upon the partta.l sptclfiQ vf,l'\une of iae)h:ane 1n the liquid ph.llltf tor 'binary $Jst•• otmethane ~a, ano1i'.b.-, ,atdtS;n. hydroctu"b$n. lig'\'U'e 9 r~esent$ ~ plot of pa:rtial :apeoitic vo.l ~ of methane in the l.!quid, phas ♦ at l00°r. end a pTttUrure of )000 lbll,. pet •q• ini- versus m~lecula:t w•J.ght of the othw pa;r.a.f:f'in ~~<>~btn in bina:iry s,•te• of niet:b:~• and ethane, :propane, n-'1.m.t~e, n.,;p-.t••:• • n~h~e and de.ca.nei, For tii. pu~r• methane •1•tem ud. th• meU,.$ ..., ♦thane 1y;tem, th• points takE!ll were a:'b~v.e t.h• critical tenper~t:'\U'elt o:I. the tyst:om sa that the phase present ts mt)"tlT a matt•r o:f' definitlith This fac~ is 1ndiea.~$4 b1 dotted. linet '1p te the UM>lt¢11la.~ wetpt. et p:ropa:n•1 fh.Ei data tor methane and the nietha.ne... et.hazu,1 qs,tem were tibta.~td !10111 a. ~y•t•m stuai-4. in thi,s l,a'bGt'a tory but at Y♦t 'UllpUblishtd:• W.he da'lia :fQt the o~h.ef 'bin~ 17$t,•- were c)'btain,4 from tti:id.1.e• )1 Sag♦, IU.elc• a.nd. l,aqey (9). Xt .'tfas dec1a..i that tht o-ur-v~• to.r ~on•tant wetght per cu11n'li ine~hM.e •h~d run \br·o\'lgh \he point• corre11pond.lng. lo the meltqlllar W♦~t• ot ethane., n...bu.,an,e, n-pentane an4 deta.ne.. da,.ta we:r-e mor• pre¢1se ~han those tt>r pt~• a.n4 n...'h$ll:a.ne. ThesJ ~• da.ta for ptQJ?@~ •-• given to tl10 dgn1f1c:ant !i~e• and. ~·epresent•a work on a w'la'bl• mass, V#i.a ble ¢onip♦sit1Qn qs1,~, the data for n..-h~ did not r19p~e&enJ as c-9mpl.e t, a. Studt a$ did the test of th, .dA,.a., .,·. ,_ fQ:r methane :i.n a buiary aya\em Yert11us mol♦c'\lla.r w~tght ~fi th,. \~:• YolaUle p~att'tn1o h1°d:rQ¢9l''bon, Da\a to)' the m•thau.e wtr• ·.1:,\;~.a. t~o!ll a •unne.r ¢ox-rela.tielll b¥ Sage and Lacey -( 10). rathe:< 1re.1.l nth th(is.e pJ"$41c.ted b the paper+ ,ha ~ta. ~-• Sj.gnifiaant a.e•t-.t!e,n• from the pointii!i occw at pre·ss\U'•es ~'bove 1000 lb,. par s.q. in• in ,ht regi.Ql\ of the. mc,l~'Ular wt1gh1i of he.xAne.. At the high.or pr•H~..;s U -was d•cided. to uraw the curves ~t•~ the points •orl"espt>nding to the molecular weight of d.eea;Qe, ,as th• preseures @e app:roaohin,g the crtt. ieal p:resaurea 0£ th~ &.fat em ,m.ert tht eq:\l1l1'bl'i'WI conit•t for deoa.n.e .1& l instead of o. ltoee it :b )elieYeA that the conetanit f()t· methane ea.loulat$d. on th,e a1l8'1mpt!o~ tha.ii th• 12 .18 1,174 P're•NT• Lb ./ • Q,lti • .1.b • ol,,.t ~ {44J) ,i . ,r..!06 OJ,Jfl;> 0 ,02 178 1000 U, 02167 0 . 1)2210 O.O221/l ' • ') J6 9 ~' O. 04 J J7 , ')' ' 43/l 0 , 0?Y l >.')2:w ,. il22l 1J 0.02146 . 0'. '1 9? JOOO u.021J2 U. IJ~l?l 4000 '500 Bu.b bl• Point ( 4?8 ) {46'- ) (J l ~ ) 0 . 0 ~-'64 :J . U2?1t. O. O?614 o, o.s.n., 500 0 , 0 2?1J '"' , .o:?20 1:1 1000 0 .04146 . 02 994 J.•J22 J.J 2000 c . 1)467 ? J. f) J61O u ,021 % , 02 666 C.'"l ?9l7 C.IJ ?M.J JOOO '; . 0?60C ( : 94G) / J4 .,J ) "" iJ . •J'>Jb l . 0'1}17 '"' 12!,0 L .Q?:'l'n 0 ,04"4 0 . 0?S '9 O. IJ2.Q., :.:. O2 J.J,i 0 . 0:>445 IJ. I)2267 u . 0 2Jl6 0 .04<.'17? IJ ,022 61 v . O?Jl O 0 . 0 3704 0. 02251 0 . 0 ?7◄0 o . :1n 12 , 0?682 "° (34 00) 0 . IJ:>9 1.J Bubbl• !'o 1nt ) . {P,394 500 u . 02J86 O. W.J78 1000 .02J7l 1,00 0 . 02J.'>.', . u ::'4.J,6 2500 0 ,024 15 V, W ..lb4 .mo . fJ ?8J.J 3500 , U?67".' l l 6Jr..) l . r ••· • ) '. 0."'447 • j l l} -16'WILi II. PAR'l'UL SPIC 11IC VOWlll'.S 01" lll'!'l'!IAD IR TIil! Ll<tl)ID PIU.51! OP TRI IIET!WIX-DIC#JI!! STSTEII Weight Per Cent llethnne a■ J'ollowe , ,. Temp. 0 4 8 10 l?..5 • 15 Bubble Point o.oso2• 0. 0619 0 . 05;)3 0.0539 0.0546 0.0554 500 0.0495 Pre ■ aure Lb./oq.in. .A.b ■ olute ,0 100 1000 o .0488 0 .0518 1500 0.0482 0.0508 0.0477 0 .0499 2500 0.0472 0.0492 O.C617 0 . 0532 3000 o.0468 0 .0486 0 .0506 0.0519 0 .05J6 3500 0,0464 0 .0479 0,0497 0.0506 0.0522 0.0538 4000 0,0460 0 .047J 0,0489 0,0498 0 .0509 0,0520 4500 0 ,0456 0 .0468 0 . 0482 0 .0488 0,0496 0.0503 Bubble Point 0.0524 0, 0547 0,0569 U.0579 0 .0692 0.0603 500 0,0517 1000 0.0510 1500 0.0503 2000 0.0497 0 .0524 0,0568 2500 0 .0491 0.0515 0 , 0 548 0 .0572 3()0(l n .04R5 n.0507 n. 0531 n.nf..,:;,1 o .0499 0 .0519 0 .0534 U,0555 0 .0509 0,0521 0 , 0536 0 , 0560 0 .0521 0.05J6 0 ,0724 3500 4000 160 250 11 0,0479 0 , 0473 0 ,0535 0 . {>491 n .r1f.A4 4500 0 ,0467 o .0484 0 , 0501 0 ,0510 Bubble Point n. 0575 0 .0598 o . 00:'?6 0 . 0650 0 , 061l5 500 220 0,0529 2000 0.0587 0 .0563 1000 U,0552 1500 0 . 0541 0 , 0589 2000 o . 0531 0 : 0574 2500 0 . 0521 0.0561 0.0610 3000 0.0512 0 .0548 U.0592 0,0626 0 .0684 3500 0,0504 0 . 05;;6 U.0575 l) . OGOJ 0 ,0649 4000 o .0497 0 ,05;:5 1 ). 0560 '). 058?. 0 ,0617 0 , 0662 4500 u.0490 v . 0515' 0 . 0 545 C. 0562 <l , 05117 0 ,0621 Bubble Point o.0621 o .0657 d.0700 0 . 0 7 ?.5 o.0765 0 . 0 835 500 0 . 0607 U.07 06 1000 0 .0595 1500 0.05BJ 2000 0.0571 0 . 06.JJ ? 500 0.0559 0, 0616 3000 D.0548 0 . 060 1 ' ), 0663 o . o ?~J 3500 0 . 0537 u . 0!>85 0 , 0640 O. tJ675 o. <.na.? 0 .0834 4000 0 ,0526 0 . 0570 U. 0618 o .0650 0 . 070,, 0 , 07?0 4500 0 ,051 6 0 . 0556 o . 0598 ll . 0627 0 . 0 67? 0 .0725 Bubble Point 0 . 064 7 0 . 0679 O.O?J:? o.0763 0 , 0815 0,0898 V, 06o0 0 . 06B!l 500 0.0632 1000 0 . 0618 1500 0 ,0605 2000 9.05~)J o . 0655 2500 0 . 05/lO 0 .0637 0 . 0722 3000 0 .0568 0. 06 19 0, 0697 0 . 0 745 35()() 0 . 0555 0 . 060~ 0.()673 O.<Yll8 0.0784 0.0896 4000 0 .054:-? 11 . 05A6 0 , 0650 _0,0690 0 : 0749 0 .0030 4500 o. 0529 0 . 05?1 o .0627 o.0663 o .0713 0. 0 770 0 . ()6 73 Ptlrtial specifi c vnlwne , cubic feet µtt r pound . 'l'ABLI III. PARTIAL SPECIFIC ',ULUl(!S or nm:.uo: lJi THE LI~UID Pl!AS!! or THE ME'l'!WIE-DEC4HE STSTJ:11 Weight Per Cent llethnne & ■ Follow ■ / 'l'emp. o r. Presll\lN Lb./aq.in. -17- 4 8 10 12.5 15 0.02153" 0 . 02121 0. 02104 0. 02082 0.02045 J.b ■ olute 70 Bubble Point 500 100 1000 0.02153 1500 0.02146 2000 0.02139 0 . 02120 2500 0.02134 0 . 02118 0 .02104 3000 0.02129 0.02115 0 .02104 0 .02087 3600 0.02124 0.02112 0,02103 0,02090 0,02057 4000 0,02119 0 ,02107 0,02099 0 ,02089 0.02067 4500 0,02114 0.02101 0,02094 0 ,02084 0,02069 Bubble Point 0,02192 0,02157 0.02137 0 ,02098 0,02029 500 1000 160 1500 0,02186 2000 0,02179 0 ,02157 2600 0.0?.172 0,02155 0,02138 3000 0 ,02164 0 , 0215.l 0 ,02140 0,02104 3500 0,02158 0 , 02150 0,02140 0 ,02118 0.02069 4000 0.02153 0,02146 0 ,02140 0 ,02124 0.02097 4500 0,02148 O, O:ll42 0,02138 0 ,02126 0 . 02102 Bubble Point 0,02262 0 , 02214 0 . 02180 0 . 021;,o o .01984 500 1000 ?,20 1500 0.02257 2000 0,02249 2500 0,02241 ~00 0 ,02232 0 .02210 0 ,02182 0. 02120 3500 0.02224 0 . 02205 0.02183 0.0214.l 0 , 01997 4000 0, 02216 0, 0219 8 0 , 02181 o . n;:'!154 0 .02085 4500 0,02207 0.02189 0,02177 0 ,02156 0 ,02104 Bubble Point 0,02342 0,02270 0.02215 0,02123 0,02004 0. 02213 500 1000 1500 0.02337 2000 0.02326 2500 0 .02315 0,02269 3000 0.02~3 0,02267 0 , 02227 3500 0.02290 0,02262 0 , 02228 0 ,02149 4000 0 .02282 0,02256 0,02224 0.02168 0 ,02066 4500 0.02275 0,02249 0.02220 0 , 02177 0.02083 a Partial ■pecific Tolume, cubic feet per pound. 0.029 ai _J oc 0.028 w a. I-' I,.. ::5 u w 0.021 ::; ::, _J ~ u ;;: uw 0.026 a. <fl 0.025 PRESSURE 1ic:• 3• LB. PER SQ. IN. t11othermal pres-ewe volume Q'Qr"l'el for a meth.an,... de.cane mixtwce 0,9n tain!ng 12. 1$ weight. per cent 12.5 w z 10.0 <{ ...wI ::; ...z w u 7.5 0:: w a. 5.0 0 500 1000 1500 PRESSURE Fig. 4-. 2000 2500 3000 LB. •PER SQ. IN. lhl'bbl.e point ~•~•iUo:n ver-au, pr~~e ttllt th:e inethane,.d♦o1.llle eys.\e.in. ai ...J a: ~ 0,028 I-' ":::j \,) ~ 0,026 1--- - + -j_J__- ,1--+-.::;'------+-,l:..._-~Jk::::::,,: ~~'--l---__...J 3 ~ \,) c:: 8 0.0241-1-==t?~7::'.:Sr:5....C::::::::_+-- - -l - - - - - - + - - - a.. <fl 2.5 5.0 7.5 10.0 12.5 WEIGHT PER CENT METHANE fig• ;. Specific -.ol•• ot the 111$thane--decan:e ..,..r,tem a.t a, ~eti~ of coBlP4•Uton a\ i6o•Ji; 6000 i d 5000 <f) a:: w c.. al ...J 4 000 ~ c.. 500 1000 PRESSURE fig. 6. 1500 2 0 00 LB. PER SQ. IN. ~essure 11 $.me$ th~ eq'11libriuxn eontt$lt as a. fU1>le·tion of pre;:;sw& for tle ~t,hane.""d.a4az>.♦ 11•t~-. ai ai ...J ...J Q: a: w a. w a. ,.., u. ,.., 0.06 u. ::l :::, u u w w ::; ::; :, ...J ~ u - + - - -- 0.05 -1----__J 0.024 3 ~ u ;;: ;;: u w a. DECANE <I) u W _ ___, 0.022 ...J a. <I) ,...~ -,: ~ Q: a: ~ ~ L------'2._5_ _ _5.L.0_ _ _ _7_L5_ _ _1...10._0 ___ 12.l .5_ _~,.j 0.0 2 0 WEIGHT PER CENT METHANE ,. r . Fig, 7. - ---·.... Partial !Pecific vo.lwne.s f@r metha.ne and, for deca.ne as a f'!lnction of composition £.or- th& -0 .02 -------------~ .,.,•',. ~ ~~ 12.,·{ \ I/ - ' 1 . 0 .01 0 Jr-:tg. 8.. \ 2000 PRE5 5URE L6. PE R 5 Q. IN. partial sJeeifi.e v:~lwne Qf de".l!a;lle u a. fu~t.i~:n o.i' preSs'3.l"e tor the roethan...,deo·@e ijf\'item ·a t l 60•J.• ) \ 0 , '\\ \\ ,~, ,~'\\:, ,' '\\ \\' ,, \ ' \.,,: \~~ • ~ ~ ~ :::::::--- 101 •t ox 0 25 ,o " MOL ECULAR WEI GHT .I (__ .J ig. 9. .J Partial wp,n if :le Y(.)l'Ullle ol metha.ne at ioo~y. alld 3000 lb.111 • .,1>er sq- il4 as a t'tm0Uon ~t ~l~~ wd,tht et. t h~ lelt vQla1;.i,.'.l..e e,m-s:tt'W,~nt tcr bina:i'f e11tems ot methane and a. teeend. pal"a.fftnic SOO ' LB. PE~ SQ . IN. V / / / I ' ' / "' / -------- - . I 1/ / -------I / --------/ ,000 """ i----:- 2000 / I / / " MOLECULAR ,,,,--- »oo ~ ,oo WEIGHT "' "' of the molecular weight of t he lees volatile. constituent i'or binary systems of me'than e and. a. 1~ X.e,rit and Randall~ TherU10dyna.mlo11h P• 22lt MoGra...,.Ht1l, J .,Y~, 2. Young, J_, Qhem. S:OCi!_ !\I•: 640 (18S5) ;.. :Bahlke ant Kav, Ind. Eng~ Ohe!ll.t 1,~; a. 291 (1932) 4, ~Ug£fi Sto:neili and Volan1e, l'bta~ J.2,, 12$ (1933) 5. $age. w,e'bitet- $id :taoer. nu... _u, 65a (19:,'7) 6. :ooss, :Phyateal Gens t~ts. o.t the hin.ei.paJ. H1df ♦¢.U.:b~n••· Tee.hnhal and letearch - Dirls1on ot th♦ Tex&li Ooq,an, {1939) Qhem. 13-(>e. !2• ll,74 (19a7) 7. :Bridgeinan, J •. • g. Lewi• and ian4all._ . !hetmod1'na.mie,s • P•· 38, le~aw.,.:~nll., N.• y., 1923 9. Sage* Jiolt't a.ud Latty. l1,ep:r'-1lt. of paper !Qt' present-a,,1,n at \b..e Eighth ~1-d Yea.r i$ti1mg, ,A?irertoan Petr-olt'Ulll tnatit~tt, M~ ~4• 193.S 10. S~e and tae•y. lna. ~ -j j Che~ l.Q~ :t296 (193.8) -M!RO!La½l!l'l'~This st.:udy- wat made po., sible through the tinar)c'ial aut.1Uian¢:• -o f the AJneric.an Pet.rel.~ Ins.\ i tute as· pa.rt of Re.i ltatth ·, tQJ•c) 37 t t. whh to expr,•• tf1l pertonAl ~~• to nr.- l• .lf•.· Sage aAd Dr♦. tf.- 'N1t Lacey tor their $ncowage~t &nd •••1ata.nt1 i.n the pr ♦para\.l~ o.f thta pap~. The work; -~ f .Jame• Jeynold• in malting tht •••rtm~tAl it''Wlfl and. ill Laube l\eanfli1 appreciated. in pwf'atming the o•lo\ila.tlQnt i, gx.-~:s.t.ly