Volumetric Behavior of Liquid Mixtures of Propane and n-Pentane Citation Hinds, George Putnam, Jr. (1939) Volumetric Behavior of Liquid Mixtures of Propane and n-Pentane. Master's thesis, California Institute of Technology. doi:10.7907/egvm-qc39. https://resolver.caltech.edu/CaltechTHESIS:12122024-234649297 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 UNSPECIFIED Record Number: CaltechTHESIS:12122024-234649297 Persistent URL: https://resolver.caltech.edu/CaltechTHESIS:12122024-234649297 DOI: 10.7907/egvm-qc39 Default Usage Policy: No commercial reproduction, distribution, display or performance rights in this work are provided. ID Code: 16921 Collection: CaltechTHESIS Deposited By: Benjamin Perez Deposited On: 17 Dec 2024 00:16 Last Modified: 27 Mar 2025 17:31 Thesis Files PDF - Final Version See Usage Policy. 16MB Repository Staff Only: item control page

VOLU?.!ETRIC BEHAVIOR OF LIQUID MIXTURES OF PROPAl!tE AND n•PENfANE flleeis by G. P. Hinda. Jr. In l?a.r t1al Fulfllme.n t Of the Requ1rementa for the Degree ot Master of Science Cal1forn1a Institute of Technology Pasadena, ca11rorn1a 19}9 CONTB.'NTB I NTRO.DUCT ION l fi ii,b' JLTE •----•-•--.- ...... ---------•---·- ...... •--- 29 DA '.r.A. INTH OOUCTI ON In the d,esign of modern petroleum refining equipment, a know ... ledge of' the volumetric a:nd phase behavior of hydrocarbon systems is us~ful. It aids in the prediction o:f capacities a.n.d the pressures and tempE:ratures o:f operation in si tuatio:ns for which no experience is available •. At present there is no universally applicable ,nE:thod f'or the determination ot' these data from the behavior of the pure components ·which compose the system •. Consequently investigations of individual systems is necessary in many cases aud much work of this sort remains to te done., However, the e ~'tperimental imestigation of the properties of' a multico mponent hydrocarbon sy s tem, one of n co.nponenta, is difficult, due to the large number of' variables which must be fixed to determine the state of the system, the exact number being g iven by the phase rule., 'I'hen, too, the comv ositions or: the phases must be deter mined and wh€n the compor1ents are many and closely related the necessa.I'Y analysis becomes com:pli•• It is fortunate that, in many cases, data obtained from studies of' binary ,~1ixtures can. be applied to more c o;:nplex systems. E1i.gineering accuracy can usually be obtained in the use of' volumetric and phase data for one componE,nt f'rom a bina:r·y mixture investigation to predict the behavior of tl1at component in a more complex system, provided the averag E rnolecu.Jar weight of the other co.mponents pres ent is similar in the two mixtures. Correl a. tion of phase and volumetric prop erties f'or one co mponent 2. against the average moleculf.l.r weight of the other substances present is frequently used in the case of naturally occuriiig oils, :t'or which an exact analJsis ·would be very l aborious to obtain •. Volumetric data are convenientl;y re i.;orted ei t.her as densities or as specific volmnes, usually of the sy::.:tem as a. whole, though in some cases th ese quantities are obtained for each phase. Throughout tins thesis specific volu:nes are reported in cubic feet per pound. T11e specific volume of' a ;:mbstance is defined a.sits volume at the existing pressure and temperature, divided by its weight. The symbols used to represent ti.I.is quantity and others of' importance in this discussion are tabulated be low. P Pressure, po u.nds per square i nch absolu.te- T Absolute teLc1;)erat.ur-e, degrees Hankine. t Temperature, degrees F. V Specif:'ic volume, cubic feet per po0.nd. y1 Mole :fraction of conponant 1 in the gas phase. x1 Mole :fraction of componu1t 1 in th€ liquid phase. K1 ·r he nequilibrium c 0nstant" for coinponEnt l(= ;:1/xi). Component 1 is t aken at; the more volatile component. n1 Mole f'raction oi.' com,)onent 1 in the system. V1 Spec i:f'ic volumE' of c omyonent 1 ::: ( c> y_/ o m1) PTna in cubic feet per po und. V Total volume:, cubic feet. m1 Weight of comp ommt l b Speci:fic gas const~t. added. U Int.e rnal energy of a system. THEORY According to the Phase rule (li' : C - P + 2) a binary system in the single vhase region has three degrees of' freedom, a.oo requires the determination of' three variables to f'ix the inte.r:.sive proper-ties of the system. c, the nuraLer of' components, is two; .P, the nu:m.ber of' phases, is onef and thue :F, the numbE:r of degrees of freedom, equals 2 - l + 2, or three. Those variables ,nost cummonly specified are pressure, temperature, and compoisi tion, usually of' the system as a whole. A binary mixture o:f fixed compositi . n is generally considered as a definite and independent system, becau1:2e it.a properties usually cannot be predicted from those of its constitu€nts. 'I'hus relationships between pressure, volume and temperature :for pure substances are oi: little use in determining these properties f 'or bin.ary sy~,- tems. Mar:iy correlations have ·been attempted bet.ween temperature, pre~Jsure and volume of a substa.nce or :11ixture in th€ gas phase. Th€ most common of' these is the classical gas law, which rn.ay be expressed in e:n.gir.i.eer•ing 1..uuts by the equa... tion PV z bt, vd:1ere b is th€: universftl or molar gas constant divided by the mulecuLir 1.;;,eight o1~ thE1 gas. ThiB relation holds fairly well f'or hydrocarbon gases at condit.Ln:i.s far re,noved from their critical states, but breaks dov~n bad.1.y as the criti ca l region is approached. Refi riemE:nts, such as those 01· th€ vai1 d eI' Wa a ls e ,ua tio:n , impr ove the accurac J but f a il too i n the critica l reg ion . A per:fect ga s h , defined d..S one v;h ich obeys the gas l aws and for which ( a u/ a V)T .Q o, where U is th€ inte1~1al energy. For any actual gas, the idea l law bility :factor, equals PVlbT, a nd i s thus def·ined by the equa•" Z';;:: Pv/-o""aVa. and zn z PVT a /pa~AT a are also used, tlon its~l:f. b ut in ea.ch case these qua ntit, h:·s are f unctions of P , T and the c wi.p os i ti on and na ture of the gas. .Eef ore they can be d.ete1:·mi ned, tb.t:: volume of the sys tem mus t b e investigated a.s a function of these var i atiJ.es . Liquids: An ideal liqui d is defined as on€ for which (a v/ ~ P) T = O and ( 8 V/ a T) D ,I: :;; O. I"or actual liquids these rela tiollS do not hold , since as the tempcratur~ increa ses , the i s othE:. rmal c 0.mpressibili ty, - ( 8 v/ o P)r,"' ' incre a s e s but decreases as P ..L increa ses. a \/ ls' or hydroc o..rbons in g eneral, ( a (n ) p )p a T = is n'ega.ti ve •. a p At high pressure s and low temperatures, actual l iquids a_;,:,iJroa.ch i deal b-el:.a.v :;.or. Correction factors of various ki nds h ave be:en applied to liquid volumes, but in each case the volume must be deter mined as a function of pressure, temperature and c ompos i tion. At low pressures the a dditive volurne rela- tion, V z n1 V1 + (1 - ni) Va, applies :fairly well for liquids, where n 1 i ~, the weight fraction of comp on 12nt 1 in the ;:;id:xtureJ V1 , is the specific volume cf that cornp onent in tbe pure state; and V is the spec if ic volume of the mi:r.:ture • Thi.$ 1•u.le fails in the cri t1.cal region, w:i.d. does :not &p1; ly to as .s;ociating substances. A 8imilar relation Wl'.lich applies quantitatively results when partial volumes oi' each co mp onent are subst,i tuted for spec if'ic volU:i,'lH~S, but to obta..1.n these partials, the volume of the rni.x-... ture m4st be deter.mined as a function o:f P, T, and composit~i.on. tem behaves like a pure substance; t ut in the two•phase region differences begin to appe:tw. of the rel ations of thrE':H~ v ariab les, solid :figures are necee ... sa:ry and these are difficult to construct, a. set of curves is commonly used. To depic·t the volumetI'ic behavior of a system of' fixed com.position, curves of' pr Eoss:ure vs. volume, tempera• ture vs. volum.e ,3.nd pressure vs. tenrperature are suf't"'icieut. On V-P and V-T diagranlS, ( o vi@ T) Pn1 and ( 9 v/ 9 P) 'fn1, thE; slopes of the isobars and isotherms, change abruptly at two points, the dev; point and. the bubble po .,_nt ol' the sy~.t.em. The state at wl'nch the system is e:nti.rfd,Y gaseous but in equilibrium w1.th an i:n:finitesi:mal a1,1ount of· liquid is knuwn as the dew point, and the ;.;;tute at i.:; h.i..ch the system is €ntirely liquid but in equilibrium wit11 an ini'i:nitesimal arnount of gas .,;.s known as the bubble point. The properties of' tht system at tb.ese p oiL,ts ace those of' the gas or liquid at the dew or bubble point conditions. F'or such a mixture the isobars and iso• t.berm.s are not straight and horizontal between the devf and bubble points , tr..rough the two phase region, and Ums differ t'I·om ti.i.o s e of a pure substatK:e. In any given mixtur·e there are three compositions of .1.mportance: n, the cu:1111.1-; :,sition of the system us a ·whole, and x -~1nd y, the compositi::ms of t,he coexisting lic,;.uid and gas phases respE,ct ivel.y . Ynowledge o:t' th.ee.e two latter quantities is frequent].J of' importance. which i i::: often Cc.1.lJ0d the II The rat~o of e,:;;.ui.l:Lbrium crJnsta.nt 11 , K. This qi..i.anti ty is a f'unc t io:n of the p:ressu:ce, temperdt.1re , ~mu nature of the ~ys tem consid12red, ru1d is not in ar.J.Y· s ense a constant. At a cor:.sta:nt but ceases .to have any mea.nir.ig ·1Pih4:Hi. the pressure beco:,_nes less t.han the dew point p::ce.ssure of the mi::rrtu.r•e under c,J:n.sideration. As P approaches the dev,: point pressure, K1 bec otn€$ :lndetermi- nate. When the pressur·e equals thi: : va:;.)or pressur e of the more volatile c:or.st ituen.t, K1 equals ur..ity. Eq.;.i l.i br ium const:3,nts f'or a substa.i'"i.CE:: a .r e applicatle u:nly in systems simi ... lar to those ir:i. which they v,,ez·e de:te1·mined., t.l:.u.s li:niti:r.i& their Thi$ critical point of' a system is defined as that state a t ·d1ich all the intensive propE::cties oi' ti.Le coexisting :ph 3.,s~s become continuously identical• ~'or binary a:nd mul ticoJn:ponent systems i t is not necessarily the point of l1ighest 1)ressure or te.mperatur-t:: for the exi2<tance of two phases in a ,,lixture of' fixed c o:nrosition. I t will be noted on the· than th€ crit.ic;a1 temperature. est at which two phases can ex.i.st in a mi:xturt!: of the parti.,;. cul.1r c o;aposition cons idered, and is known a. ;;;.. tha criconden ... t,her::u.. It is in no sense a cri ticaJ. point: for the proper-t,1es of' the t 1,.o phases are not identic a.1. It will be noted also, that if the _pressure is continually decreased at a c onstar1t tem.;::erature t:tbo :.re the critical ten:rpcrature ~:but below the cri-. and tlle i s othe;r•m in question crosses the dew point curve in two places. _This phenomenon is called r E-:tro&Tade c o.r.i.densa• tior1, -:and occm"s i n tl:l.e t wo-pha se region of a binar;y sys tem at te.wp era. tur es above that of the e:r.;,,tica.l st.:,te . Two generaJ. t ypes of apparatus have been u.sed for the measu.remEm.t of the pressure -v olu:ne•tem1.;er.ertur·e r e lations of hyd:cocarbon systems. Thesis utilize the same _;)rinciple, dif- fer..i.ng only in :nat€rial of conetruct.1 0n . In €ffect, both er.::n.1.sis t of a chamber ·which can be .ma:;.nt,ained at a constant tem.psrature, v/r;.ile the volume is cl"J. ;1.:nged, t.he pressurE. a:u.d v olume being mea.erur~d . In one of th ese devices the ch..'tillber is o:f stef.:li (l)*, wbile in the other it co nsists of a glass capillary tube, sea.le6. a t the u:pper end (2,3,4). 'l'he steel apparatus is capable of c a.rrying on i nvestigatio.ns at 1,ressures far in excess oi' tho s e which are possible in a gla.ss tube. ThE- g-r•E:J.ter vol.u:ne of this type of chamber make~; pus i,iule the use of a l a r·gE!r sample. However dew and bubble po .L.nts can be de termined only lry locat i :ng breaks i n the :i. so t herms and iso- bars, a procedure which becoxI,e s so di:ffJ..c.ult as to be nearly .im.i.,t}SS.ible in the critical region. Since the sarnplb may be seen in the glass tube, dew and bubble points can be loc a ted vj,_suall y, ..md the number of' phases present is knowr1 at, all times. This is not always the cas e with the steel equipment. The apparatus used in the 'Jrnrk he,re re yorted utili z.es a glass capillary tube. 'T his apparatus cG.nsists in e s sence of a thiek-·walled glass :K Literature references a.re J.isted at the end of this thesis. ® [liAl, riA /'1 ot 5Yj7[ M '"' VAl?YING pend V f-"J l ~wd Confoc T Gu.~ ,-1.,...__,,....~,. T,,b,@ lo A=,,,-, L,ne h) lo hcra!or1 '"'"- Avnp J;; R,,,..,.. TanA. Hy ~ ~ rllOlr ® 7;, G.: .,.'f,e ® ----- (}-"A., ® ® e @ ® lo Figure 1. Diagram c-,. of system for varying pressure and volume of sample. a. steE.l chamber a t the lo,;, :er end. This ch hillLET connects to also to a dev lee for mf;<'H:iur ing the: pressure , ;\round the outside of the glz,.;.ss tu'be is a glass j a c ke t, iivi thin which a .,;:-,t1re Eutstance is b ,i ile-d , By mHlns of a;,.1,t ,)ma.tic Vct lves, the pressure:· Li. hove the b oiling lh;Llid is ma intained constar;,t and ane:. the .i.L.sio.e d ... amEter , ~3/16 inch . Tht upper end i.s sealed oft: in s0.ch a ;:na.m2er th at the t h .. ci-,nEcs-s of gLt85 at th€ end i b thf saifa€ as thE: wa-'l tlL.c k ness, in o:rder to avoJ.d u.nn.eces- op0n end oi t.hE t .uLe is ex panded to a thinner -. .a.1.it::d C,ilinder 0 1 1/<1 J.nChcs in -,:;, utside diameter, ar:d l 7/8 :i.nches long. h E,fer1.-1.ng to tllt' dia.g:ram of the syste:il sl1uwn in li'i gure J these It will be notE; d 1n th e same diagram., that the large uid B of th € press ure tube: f'J.ts snugly into a. s teel sh€J.l. c, V-JLie:h is a JY.:L., t of the cov.sr-- of t h€ steE:l chamber . A ri.i.bber washer D, protectb tL.E; top oi th€ Enla::·gcd gla.6$ cection t·r·om a ctual c ontact, \;J. U, the st.l"_,el . cover t-J a.ti 3.rrangement si 11.i.lar· t o thE: pac .k.i ng of a valve . aga;;..nst the tube by a pac king gla.:nd. F' , 1'orc1Scl ( :t .v,n by- a t{L:J.nd nut As .in the c-3.::::e of a valve stem, th€ pac ki ng g l u.nd a nd t h E; seat oi" thE g a s t:;f:: t t;..l.be ru,.d ei'i'ccts a t J.ght in the cover a re bev eled so ti1<.lt cl o&ure . I n tightening the gl.and nut, c :.:~re i t re q u_;_r ed l .n order to SW ;.;id develo:::,ing strESSts.:s The c o v Er .d1t0 wl:.. i.ch the t ub€ i s c onne ct E.d .1.s h Eld t i ghtly t o the st E:(:l Cl:i.-;;;ubcr by s te El tolts H, ar..t.:i a ;.n.or:tel mc t a. i g a Gke t I ,. betwE.E.n cov<::r and A s:nall p assage c :)rnH cts t Lls cha.mbo· v: .;. th ::i s,nallEr- c ur.tact charftu· J , i n an cxtent ion on t Le Lott ..,m or the steel b lock. th .J.t \\hn1 mercLlr,y ri1:>e s t c t his level , a ci:r-c~dt is clo sed and Fro:11 the b ot t o:u of' t h i s e: 0nt ,. . . ct way c onne ction L. This lir}~ i s broL>.ght d.v wn belov,· th.<:: c on- nee tion and bac k u.p t (1 it , f c-r 1.ai:.:i8· a tra . , and thus p rev ent ing c onnect ion L, one line lc t::1.ds to a pressure gauge , so t liat the p re sc:,ur € on the: me1:•c ;.ir:i at t h is r oint ( wh _;_ ch normally is near·l:1 the sam.E. as tlr:it vu.thir1 th e pr essu.r£ tube) can be approximately measu.red. Another J.ine leach ; thru a n1::, ed:.Le v aJ..ve lfl , s1.ightly upward into the bott ::i,n o:f the, :nercury rese:r-vc ir N. This re- ot: th.is part of' the SJ Lte.n , so th a.t any ,:.tir l...t:i.sJ.t leaks in will ri:.-:,e into the- re f,er'V :.: - ir ) f r ,; il whic h it c an be rc,uoved WJ..th out d.;_i'ficu:i..ty . 'I' hf: f o ..;.r-th line i'i· orn th€ c oLJ.1€ c ti on le ads to a te E o, f'r om which branch ; i pes to the presr . . . x·e balance c ,.-ntact c hami.)er P and the rna.n -meter Q• Valves R, s, and 'l', make it p ossible to shut off E,..Lther or L=Jth o:C these Th t"! ;:n ercury rese:.cv0ir Ir is a heavy ... walled steE.l C,\/ lino.er, vi i.th a g~skbteci t op bolted to tt . ~~t eel tuL.1r~ leads from the top oi' t h lb ch_,_rnLE;r to the w..:1.lvE sys te:n 7J, V , \~, and x. This v a c u.ur:i to the resE.:r·vo ir • .su.~-e c __._ rried in them ·w hic h wou.ld. make regulation ci:ffic~i-t, and. :n:;.ght. damagE the apparsltus in eve·nt oi th t-c 10. .ilure cf a valve . ConrH:Ction to the p:cese,ure tank is mad.e l,etv.-ce:n valv es Valv e :x was or:i.gi:n.al ly used for .inf'lat.i.ng th~ pr es- sure ta~:J( :f r ,u 1 the prfa;: s:.i.r e :u.:nE;S , but th.i.s com1cction has beE n disc . .nt inued and it is no long er neces\sary . Valve W t o bl eed do'I.H"l the systG:•i tl to .;, t,.i w~,pl'1eric pr·e s su.re ana V).lve U t h e l abur-,:,.t ory v a.cu.um ,CU inp :i.n C H. S e pres sures be.lo·w atmospheric a re defd.r ed . Th e pr es i:::.urE:' c:x.Lst:i.ng va thir:. the syst E'I.tl is mt-:isure-d on a. pres.sure balanc E, r·eudJ..ng to o. 01 pound per squa re inch. copper tuL:i. ng line conta::.ni:n;; J l.L connE-cts A this bci1.uncE: w:.i..th t h e C(mt act c.1:'1.:::1..mbtr P. ·vVi th a V;-;j.p or bath c ontai:n1.ng a 1~.ure l.i-. _uid bo.il:.i..ng at a c ,n1st cint pressure , is a djusted by va r ying the prE:Jsure . di ..,,.t-: ;r cwi of t he t u1,p er:1t:ure c ... tr ol system _;. ; res€nteu in .f igure i). . ThE space Letwe0n the 'llval.ls i.s evacuatEd to rn.:...nimizc con- duct,ion lo ::. ses and. the _;_ n~; ide a nd outs1.de Vi&\l..LS of' t h is s pace a.re silvered t o l ' €ducE rad..iation lo c ses . i\n un~ ... lvered. strip z,pace a1:ov<2 t hE: l.iq \..cid wi th a Cenco pw.np . Ee:f erer:..ce to ,1~ U- t ube B , c onta:i.n.1.: .-: .g merc..;.ry , i£ con- HE cted at one end t o tht line l ,.:.,J,ding fr .J,n the v acuum :pi.llnp to -U1e j ., _ c kE·t, ·wi:1 i le the other end. leads to a charaber C, which r t- l L - if L ~.,-- N I IJ [' DD ,,, Ii I 1-i..., u/ , r Ml'f 1,111 uNt 1.. otV !!1' 11 SY..;11f/'I Figure 2. Diagram of temperature control system. 14 .. is a l1rge se ..l ed g l a ss tube. thru t he stop cock off . The tv.rn arms a:cc c onmscte:d in t.hE j ... cket , as Eurt,her operation of' t he :,_) u:mp c auses the mercur·;;x in t h e j :::i.c ke t arm o:f t.he U tub e to be forte.ct up by the 0r·eater p:r· t:.s s.. u.r€ in t he d:i. i2L1ril:er sea led ..1.nto th t:: tu.Le . and t o rn:1ke co ntact with a. \Ur e :G , TL.i s c 0mpl i:: tes ~,u1 elGctric a l operat.J.ng :1. rela.;y· which c c.r.tr uls a rrisrcury switc h . c:i..r·cuit, 'l'he closing oi' this swi.tc L allov-, s current to flow thru the c-uils of a s -~;lono id F , wl u..ch activat es a magnetic Vd. lve. :field produced lifts a valve stern and per:aits air to bleed into t i.le s;y·ste:.a , incr easil.:g t he press ,1.re and f'or c.1. n.s- the mercurJ d ow~~ , aw3.J fru:.n the c ontact, thus Lreak i ng the ci1·cu:i.t. The ste:n the £:;. u !' Jr• S back i nto p l a ce, stopp ing the a dmitt ance of air , arni t he v ac u..um pu.I!rp ev acuates th~ jack.Et unt i l the prace ~s is repea ted • by c o _,.trolling t he rate 01· p1 ·es s~'E .i.nc:cE. ,,_ae ,.·'..i. nCL rc: ,:L_,cti.on thr·u v alv es G and H, mov ement c t the i\ c uLde~ :.ISfl' .ils ~tta cL€d to the top of the j a.c kc t, to c on.- This .J..S done no-c, 0111y to c ,;nsE:r ve t hE: 1iq_u.id being boiled, but also t o p : e- The trap 1~ , serves as a i't.u:·ther pre<:: _iu.t.i on aga}_n s t t h e boil .... .g over o.f ' l ..l..quid f r· o1n the b ath. 15. in thE v:tc ..,.w11 s;n,i tem to reduce the ., ul.s at.10.£ produ.e:ed by The i::' topcock O i:.k.t,Y be Ud:,d. to ]:Jr event .;noveiu.e:nt of th1,:; :ne:ccury .in tb.e U tut e L . The ,c:nergy li.Lcessar,/ for boiling thE: li '-,.0. .i.. ds in the vap or ba.th is supplie,d by an electric al he ,it0,r L, wh ..i..Ch. f'i.'ts around t.Le bott vm. of the j a ci~.et Lelow the du,_,ble walls. hes.i.st.a.:nc es in series with t h e hE; ,:i.:ter allow the rate of heat.d:.g to be c011'' Bu.mp ir:ign o:r.' UH:: boil:i.r~_; liquids is av ,~ided by To prevent to thE Lott-_; n1 of th E. toiler . J\ 1:1 :,1all ·water co oler b~low the the outside of th<~ bctt ,:i:n of the j a ckE:t and OV6l' the pressure The lntrod~ction of Slt:f:(icient ;nercu.ry· t.o cover tt.. i.s seal ;i1·otects thE rul:::ber fru :-n the orgaL.lc J.iquici.s which are The stopcoc k P e:nctbles t.Le - liqu:Ld. to be drawn off, ·~;L.d.c stcpcock :·: se:cves to re:1 ie:ve the vacuU.ill in the j ·:.. cLet. Srna.Ll tempE:ra.ture changt:::s are ms.de vil"Lile t ht co~~tr ol mercury- i.n th€ manostat ty :llt ans ot' an a......xiliary valve J, 16. co:rmectH.c to a linE" f'uJ.l c f mercu:t''Y ,.._1:d loc,J .ted ,.nore than 7 6 e: ,: nti21eters below t.11(:2 lev e l o:C the ,rit:rcu.ry in th€, U tube. ,.. ::.d tht.1s incre s1se s tl:..e pres..su.r-e in th€ j -;.ic k et; turning i t outwa:cd has t1:.c o;:.cpoei te ei':fect . The te.w.pe·ratur e e:x.;.stin,g in the va_,. or b.:;i: th is .:J1€:asured and it is l ,Elj.cv , d. that thE ternpEr a tm·e ·w i thin the vapor bat h v,aE det frmil~ed t o . . ..i.tLin a tenth 01· a degree rela t.i..ve to the Although i rrto the J• .i.c ket tetv<'ccn thE bo :;.1u1.:· r.::, lio.uid J. of f' into the ., .ump. rangef::i for which they are f,Jund s .,;.it at.le are; 17. 1 00-1?0° li· 'I' o lu.enc , C. P . Ch 1orobenzenE265- 300° PropH' ag.:i. t2a.tion of th~ sa:,ip l 1:. ~:,i tl.u.n tht pr0ss ure t ube i G essentia.l to aGr::ur'E'.: th€ s.ttairnue.,.l.t of E. (-;.•-d..l..t.br.Lum n o d.ire ct mt:~cha:r.ic al r,t :i rrer can be c onvientl~• e ,riplo,y-ed. the t ubE . Co11- l B. To ;nakf.: po ssible \.:he a.clCU. tion 01 samp les A built,.. t he v ;.:i.c uiJJil side of' th.1.s V -A lVe thE:ri' c am_ p J.. E i:: omb co nnect.Lon on t he :c igh t is a passage lc:;adi.£ i.g to theof t l1e bloc k . The vacuwn L a c Led up b~r a CE;HCO Esvac _p w.:-:np , and t he f:::JS tE.o.,t ic. C.:. . p2:.ble of proctuciL,€ v a cua of t..ii t .ma.g:.1. t uu.E' ,:,f 10... 4. .:u.11 . 01. me:rcur·y . i:n<.iic:at t::d in Figure 1, this v a.c L,.ill.i.1 syb t1::.n a l.sc. corniects of ·tJ~E: va cuum pos s ible. s arrrple Lcrnb e: OJlne ct ion. 19. c om1ecti on. Th€ hig;h-vac uum l>U,np is then. started, errtire lint .is evacuated. •--- fo1 the V!hen a fairly high va.c ..Aurn has been attained, the pr€ssure on the mercury reservuir is rE:duced, [)lel"lWJB.ilO\'i6d to flow a nd.A out of the prt:,Bsu.re tub e and down to a pol.-:.t b E low the contact J. Val VE Z, c orrr).E:Ct J..ng the V 3.cuum line tc: the: .inside itself is evacua ted. Aft~r thE sy stem h ~s been evacuat ed to a larg e 5xte1~, it is Leing a.cided , 1111c1 re• evaci.Etted . atta.;.ned -s.Ld a 1 1 air Wh€n a high vac,J.Wi:l has been urged v '..tt of the sy ctem, tht e:h:.unber is shut off f'ro~n the vacuum pu:n:p by closi ng V-:.'tJ.ve Y, the mercury slowly to tht system. contact. the reserve.Lr H sl.ut off, th i s ,m.,:i.norrreter and. the f;re .c, sure tube itself :f orm a U tute, tll.c pressure on each arm. of v.,.cich ~i t l,h.e 'teginning of adnission is the same. however the gas i.n ti1e 20. c u.rJ to l'lse .1.1:. the u-t h er Jr ,il . Ey aci.r;.itting rnercury and thus ar.:.. • estim~.1 t.1:: of the a:i1 0..:mt of sample addtd can be made :from t Le 1;:ires cu:re ex.;. f>ting in the ,., ,Jrk.ing section. ·r 11en suf:t'icient the ~ressure tube c ·,.,oled with l.iq ul. d a.i..r , in order· to c ui,ciense wett ., .ng tho tube v.~~n.s and i,1Fr-cur'J/ ·w i t h t···_J:, :r.y droc .,rbcn. Lef'or e cooling howevev, valve Z iE:, clo s ed. bro ught up earn:ple thtn.1. e:001£6. in li c:ui d r,. ir, a.nd the v ,.lve rc,op enE,d to the CQnnee t ing :u.ne, so that the hyfu•oc a rb on r emain.Lng in the line ver;/ low. The t,o:nb VJ.lve ir ther:. closc;,d, ;Rnd t-L E b,L-tL r e:moved 21. it is :frozen at th-:: top wh:l.le the ot.hc:c i:a teirig 81:'.tded . All ac.ditl.ons of' samples are carried out with the vu;.por jacket The volume oc cupiE)d by the sa::nple was frum. thE. sealed end of" the tu.be .. o:t t.hE:: t,auce , t.1i.;,f; 'l'he v.fas calitrated as a f\,.nct:ion of tL,. s Bowevel' instead o:t' plott .Lc.g these qua:n:t..J..t..J.es , one a.s a fur1et.i.on of the othEr, it i16 :::10:re d,ccur::ttE t.o determine an a.yerage diam€ter- of' the tu.be, and plot I"€Sidual volumes, the This gave a smooth curve. of 0.1 millimeter. I t was found ..i.m1. rac tic al to ca..i..1brate tLe v c. •lurne o:.r. the tu.Le t.y .mov in£; a v,eighed s 10..g of !·ncrcu::."'y La.ck '::s.u.i. :t'urtl:l along Cali- den.si ty of tlie :n&r·cu. rj', tlh v0.lu:1i<: o.; tl:·.E. tu.Le as a :function of the 1E:ng tb. 01: thE: c oL. .tnn ,ras ca1cu..l.B:ted, and from tlns, rE.s.i..ci...ial :Me;rcur;y w~is th.en fore ad into the tube, the ise:1mple thoroughly agitated, an,. •. thE position of the top of the mE-'I'Cil!'Y read. with , To t 11e catnerneter•. This reading \H:'l.~, then recorded as N• It A i'oun.d C.'J!.)llVcnient to record :for each .,00eition of the mercury, H~, tl:i.e zero reading o:f the top of~ the p:.:-·essure tube, .L as ti..i ... s value vari€d with the pressure 1-n thin the tut)e. The scale rea.diug of' the pressu:J."€: baJ.ance \~;;.~.s th0n obta.i. rH;d, together 'Shen two phae:,es were present, tJ:1e technique ·was essentially w. . ti1in tht~ tube, v.as recorded, a.nd considErt1Dl,y .acre agitation and tixne for tb.e atta.l.nment of' equilibrium were necessary·. of tht phase bo~n6ary. req,.LLred. iy venting formed. At th.:.s po.Lnt the pre::csure v;as i'ixed by closing tl1c, 23. air outlet valve , and thE S:J.:nple vigorouslj' 0igitatEod. If the If' i t c o1itinued .n1 tri.E= t1ns range . app0 .tralic t ol. ctew v"\lnch did :L.ot cL;.nge i.r, ai:.:11)unt at c0;;1stant pressure 1:.e..w.,g t, ,).k:en a~; tht: criterion of their est:ib ...'i .sru:n ent . I t WEIS f o1.n10. th,,it, tb::, l,tates t h us visue.J..iy detE:r iainE,ci c0:..ncicied (fi gures 3 and 4) and convenJ.E,nt:J.y· loc ,ited th€ 1,-...i.tb:i.e p;.; .... nt P:r·essure Calcul.j,tions: -----·--=---------. . . .= measure:m.ents V>P:LS f.Lrst caJ.ibrated. aga.;.nf,t the mEcrc..i.:r-;y ,u,.:,.nomE.ter and bal.s.:nc eI m.1..ght t ,e obta.:.ne d• Thf. ec2.1e corrE:c T..ion :fictor for tnE balance c :,i .1.cuLited. su.re, g iving the c1.bsoJ.ute pressure on t h e s :;1. , ,rpl~ ih t:n.c tu.Le. AbEolv:te Pressure :;;; /..(Sc1Je + B + l::,ar -J ,ncter(Corr) .. L ( N - . :"~ ) 0 wt.E.re A i s the E:calE- c orrE:cti.on factor 01 the pre::; :.>,l.I·c b -:~lciJ.1e E:, i:-s the correct1.on f'or th€ c olu.rrm o :.:. mercury wi tlnn the pr•d:,sure tub<::. K is a con- ver s ion factor for co nverting c enti.meters o:f ,nErc ,.,r;y· to ~.:ounds ·" i u the l.Evel of the mc1•c;).r;y \L.ithin the top of tb.e tube, and B was evaluated Vvi th the 1.nerc wry at this level. As has bei:::n previously mentioned., the pos.1.tion of th~ .a1ercw.ry level in the tube was used as a :m easure of the vo lu<iic occU.f.1iEd by th0 sarrrp1e v,i thi n the tube. 'l'he length of tube ;fill Ed -wi ti1 sa31pl£ v,as obta1.ned by subtracting :,: from N,r • 01· 1-:, This quant:;.ty was either obtained :for each value o:r vu.s calculated from th~ ex1.>~ri:u1enta..Lly determir~ed relL,.ble, and ;J,as uted in the c~)@;Axta.tio:n for♦ most o:r the data Pi t.unes tb.€: squart oi' the average rad ... us v:f the tube, giving the total appar£,nt v0lume in cutic centimeters of the space above the l-r1ercury level. :floating on th€ mercury was al.so :Li:.: tLis s;,.H1ce, its vo lu.r.ie had to be sub.tracted f'ro,.il the total to give th€ app<S!.rEnt. volu:.ne To obtain the actual v:;lume OClli.PL d th\'. 1·e.s.:i.di.li2ll volu;ne, b~l th(;; samj,1.c, f:rom Y:R 'Vi!&S su.btr•acte:d ¾correspond.ii~ to the lcsngth of tube l'i'r • N. - This auanti ty w;.:1s obtainad :t·r,;m a 1')lot oi' V - • The ~ total apparent vt.:,lu.'11€ of thE, sample, m1nus tlH 4)rvp€,r rei::.i.dual \ volu.:i.ie, gave ·the volume.; in cubic centimeters 0< cupied by the Y. multiplied by a const.1.nt ,;;.nd divided Ly tt1e we ...gLt in gr.:11.ns o:f sa.rnple \•d thin the t,ubE, gavE: V, th{; &pec.1.i'ic volu.;:ne of the .,ili:X.ture .:i.r1 cubic feet per pound . ThE: f 0:cmulae 26. usE:d were; V-c ;;: .20742 (l'lm - H) • J. -,d. .0203 .~~0?4:2 :::: Fi X (Ave. I.adius oi' TUbt:/ • 0203 :::: volum.e of stir•rer- i.ii ire• '"',11 ... N) y .... 1"'( .t~ ... .-v ; ,. V J.. .::I: -R (Determined from plot of' y vs NT - N) - ;::;V V == .01602 y/wt. ol' Samp le (gr.) .01602 = constant :for conve:rting CC/gr. to Cubic feet/pound. galcula. th,n oi' Cornposi tiora Although tb.eoret ...ca.;..ly thE:: weig.:i:ung of the hyd.roc,lr'bons as gases into the a"'.paratus should h:.we 6.eterrnincd Loth the: c um,.t;o;;,i tion and the toted. WE 1ght of th€ sarnple, it '\rVa.f; :f0und act...i.a.lly that th€ results of· this ,net.hod wu·e of' insut:t·iciH1t accuracy·, es pee iallj for t,he ver-j srnall qu,:1nt.l.t.1es nece:,ssary t .,,;; o'tta.Ln dew points at the loVl-er ternpera- tures in.this apparatus. di:t"f.Lculty, Ly rus.1.nin,g ai1 isothern1 on the r ure 1)€.ntane ir~tro- tion of any propane . ( 5) the weight of this substance pre~ent c O i.Llo. be cal.cu.La ted. It has been deter.mined ( 6) -that liquid ii1ixtures of propane and n-pentane :fc1lov. closely the laws o:f ideal svlv.:ti -.ms at low terrrp€:r a tures, .: ;,.r.id thus the additive volume law can be a;.,plied , using the specl:t'ic volwJ1es o:f the pure co:qponents (7). Appli• c a tion of this law will give the we ...ght percent of' propane present, and i'r,.~.m the knDwn ~.E ..i.ght of pentarn:', the total weight A sa'1lple calculation follows: of' thesanr_pl~ c :,.n be dE:te.rrnined.. Additive volu.:'11€ law V - specific volume W: Weight percent From th€:, volun1€ calcula tL.:inz of the apparatus: - w1/wt Vf - ,. , t,q, and I 2 W2/Wt Thus : .01602 _ v/ wt t = 130°' P z 310 . 10 lb ./ in, 0 . 03581 c:uL:i.c i't ./lb . (7) V2 -- (). ()~2692 cubic ft ./ lb . (5) V1 :::: • 03bt:31 W1 .;.. • 0~16:::.2 x . 48b4 -~ 1. 6448 x . 01602 28. W1::.:: .3710 gr. A Si.:rt~lar :·l letnod .rL:;..ght h1ve b t "· n used for deter1r1ining the. c ..:tiposi tion of the gae=.eous ~nixtures, had :i.rrntr.a,rms been run on the pentarn; added. In this case it 'vrnuld have be.,en. necess a.ry to assume that the e..ibst,.•nces behaved as an ideal s ,,-lution at i n:finite attenuation , and. thus tha t the yalue of' the c ,,a1pres8ibili ty f . .ctor, z, wa.s unity at zero pressure . Volume r.ac::;;.s :...i.:r·e:n€nts o:C th.€ se small Sa:£+ lE. .s in thE: l iquid region are not a.cc urate enough to afford a part.1cu Lu' LJ g 0od corr-~lation, as th~: length of tube occupitd by the sample ls ,rn:iall. X'h1;; culci.!.lat.:u).n of we ... ght and c :>.u1r-usi tio:n on th€ bas.1s of the corrEcted compres s.1.biiity f ',::\.ctor v, o,J. ld secI1 to b e the 1. ,-est suluti 0n to th i s problem, although c ;;mpos i tio:ns might be establioh€d by a carefully d t tcrmined curve of devi point pressure vs. compos ition at. a f i:xed temperature. Eiuch a cur·ve ii,, .)uld make pos::sible the dE:,ter min, ,.tion of the compositi 0n o:f the mixtu.re:s al rea(i:i,· irwes1.,lgatE1d for dew µo .Lri.t tut not l't;Fvrttd ht,re • I:~'fi:S tJLTS The data pre sentEd in th-1.s thesis ::\.re the resi.1lts ol' mE;,:'l.sur•ei.aents on t.h.r·e:e .uixtur·€~ of propane and n-pentane. 1'he ~1.a1ou:nt of sa:npl€ used in N1ch case prec 1uded investigation of anythi:ng: but the liquid i:ihase and bt,bble i; o.ln.t region. save i tt tempe:r• ~:i. t ures near the critical. Volume.tr i.c u.ata f'or theB€ liq_ . . . ids are presented in Table I re ,- orted as press(.,4res :for even volUill€S 2.t various tempe:ratures , and vo..a..urnes :for even Table II gives the pressur·e, te;.Uperat ..tre and vollune of· the mixtures. at ·u ubble 1:.. 0.J.llt, con.d.l tions Table III giv&s er l tical and cricondentherm d,.;.i.t 1.:t for ~Hixt....res 1 and 3 , and for even c0m1, 1 ositio11s thruout. the system. ThE: d~ta in Table I are l.LnJ..ted as. to accu.rac.;r b~l uncertainties in the: c u . .npo s1. ti on of' thE mixtures• tions t1.rc p:t·obably good to v.-.1.. th in one tenth of one pe:;.:•cent. For e:i.ch part.Lcular sybtern the error is co ;,.si6.er..:.1bly less than this, it i s believed. tione in The necessity of composition cot·rela- obta1.:a.i..1i.g part of the data o::c Table II i.ncrE'.i.:iSCd the probability of €rror, so th ,:..T. thE: Lubble _\Joint pressures at eV6n coJJ._f:; osi tions <-iI'f. proba.bl.:, accur•..1 ·~e o:u.1,/ to the ne,:l.re;.. t The critical and cr·i(;ondentherra data are prob~bly g ·,.ivd. to wi thi n 0.2 - 0.4 percent. Vap or p:ceseures and t};.e critical c ons t<.:luts of _.; . ur~ pe:r.1tane 30. were obta.1.n.ed f'roril th~ yu.blic ~tiurn:. oi' Your:Lg l 2) .. Specific vo1w:mes of th.is substance were ta,k€:n :.e':rom th€ \v;.;rk of' ~:iage Isotherms .mixture in Table I on the pressurE:-volume plane. ing :from the:: li,.,_uid into the two-phase :region. It ·wi 11 be notE d that th(:: slop0s of these isotht':rms change abruptly at t..t.i.e bubble poin~ in e~ch case. nou:nced as the e:r:ltical. region is a:;)proached wh€:r·e the pro_pe.rties of liquid and g,::ts becv,"1€ more rHJ.t:r-1y tli.E.. sam.e., will be noted too that the slo_pE;; of th€,se J..i:.Otht.1·.ms It 1.n the ture is raised. volume increase due to t11Erm.,:1.l expansion bE;ir.g .:::;I'E:i:cJ.te:r tl.. an diagrar.n) decrei;i.ses a.IS the te,1,pErature J.ncrea:~ee.,, unti 1 at tl.1.e F'igu.re 4 :i.c a. plot of the crltic :ci.1 region o:f mixture 1 on DIAIGRAM 04 300 I\I LB. P(R ,5Q . IN . PRESSURE I ' I- 500 I 600 I -- I Volume-Pressure diagram for Mixture 1 at temperatures below the critical. I\ Figure 3. 1 I .oa l - - - - W - - - - - - + - - + - - - - 1 - - - - + - + - - - - + - - - - r - - t - - - - - t - - \ - - - - t - - - - - - - , CU. FT. PER LB . V .12 l•- - - - i - - - t - - t - - t - - - - - \ t - - - - - - t - - - - - - - - \ - - ~ i - - - - - - - - - - + - - - - + - - - - - : - - ~ V- P 31. It is really a cout..i..nua- t.:i.on of Figure 3. ~.s the cr:i..tical temperature is a_;.:1;roachE:d. and exc€eded, the: lines t:h:i:-u t.ll.l.S ;;;1.rea en0v. more C-.lr'V'.:lt0.r·· e. At these teape;raturf:S thE: slo) es oi' th& isothe:ri.ns Ch.;mge Lut llttle at . ..hE dew :'!..Ud bubble :; OJ.ntE.. It can be seen th.J.t an ::.sot.hE.rm for 344 . 2° 'IJV(.UJ.d be tar~:e:n.t to the two• at v,L ~.d1 t'wo phases Cdn exl.st :for a mi x ti.lre of th.is i.:;;articular C•.:-',:1i.10s ition, a.::1d ~s several degrees a.bove thE.: cr~t ... cal 1.;u ... nt, c. 'I'he y11E.1,0menon of' rt:tro&,T i.C:i.Ec c n(~ensat i.on is we: 11 illustra t E:6. DJ {; GL..o.J.dE:rH.Lg ti:1€! isothe,.:n :t\:ir' ?4 3e, \::Li.cl'. ir:;; aLove thE, c1·i t1.cal tE ..,,1. .-ratu.re p ,xuncl s p~r square inch, increase in th€ prt::S$UI'E: ca ... bes a ~E'CI'base in vo ll..lillE of t.he g:.::.s :phaf:.;e u.nti 1 a. preseur·e o:f about recorded.. J.iri,_4id f-Lrr.;t. i.lle:rc.:.,.ses in ar:.10Lmt, a.nd thE'n ra:: .i..dl,.v- decreases , thE .mixt:..lrc rea.c.L.iLg anothe :1 dew po int .tt a.b,::;ut 6(17 P,JU:i:J.ds p€:r square inch . I?urther i.nc:r-ea.Ea,e J.n pressure dec r e-:.:..s es tl1e volume of tl1t sJ.. r,gle-pr...al;5€ materJ.al present. Wl1t tLE:.::. th.,_s material P-V DIAGRAM CRITICAL REGION MIXTURE 330 F 550 • Figure 4. PRESSURE 600 LB. PER SQ . IN. Specific volume-Pressure diagram for Mixture 1 in the critical region. 32, is liquid or gas it dii'f.J.cult to say. is above t h~ er icondenthE.cJ:•m c:tnd thu s Sl.!. .)',. s nu 6..1.sco :n:t.uiui ty o.f p hase uc t.ht pr-E:s sur-e i s increased.. d.ete:r-rni r.~.d po.Lnts were shown on t his :figure t o illustr.s.te the The difi J.cu.1ty of a \,,te mp'ti r~f t w :fix thls ci.lrve b;y· breaks in the i s othn·ins in thEc cri ti.c a l r€glon i G obvi ous. Figure 5 is a plot of bubble pc ... nt pres~ure vtrsus com:i,:io.s.i- Cor,sequently t he former c urve .LS C 0L:.tlnu 0 us across tLE diagram, ·while: t l:e l +1tter '"1erges vd.th a dew _J;)OJ.Lt et.U--vi (not 1c sta'blished) at a. cr _;_ tical co .. positi0n lower than 100%, propane . Th.E:bE: curve$ cannot cross t he cr..1.tical press<.1:ce- de·,, .;.: oint curves at th.ls p o.i.1 ..t. The -c ritic a l press1,,.;:re-com- position .curve, sho\u-1 across the top of this diagram f'orms the uppEr l Li1it for· the buLCle 2.> 01.:nt cur v es . These curves reverse c urvatur€: as the cr.it..Lc al rEgion it:; approacb:~d bec ;ming con- cave dov,nwara: :: md t angent t o the critic al locus ca l pressure. ,,: t, the crit i • At higher temp era tures the bubble pv..l..nt curves a:rc ;nore limitE.d i n ex.tent, .: nE: et:LDg the critic ,il l ocus. at CRI ICAL .,_ a(/) 0::: w 0... m _J w 0::: => (/) (/) w 0::: 0... p COMPOS! 0 Figure 5. ION MOLE FRACTION PROPANE Bubble point pressure-Compo.sit'ion diagram.. t.O 33. c o:npos.i. ti0ns luss :r· ~ch ... 1:,. propane. the thret: .;:uxtL.:ces ::::tudl.E.d, togetl:,er w.1 th th€ vapor pressu.r·e locuis of er· ... tical 1:.,0J.rr'c.s of ,:i.ll ;J1ixtu.res c.>f' j_.,ropunE:: and n- The rnax..wnu.w er i tic d.l pressurE- ls s ,.,1m€11l1A. in 0:;..-;.cess For hydr-ocarb.-n.s it has been twE:u1 the cmi.l; onu1ts, the higher will be tJ~e maxiaium crJ..tical pressurE: of thE, system produced t~- s..u.xing them. T'he. max.L.m..u.u cri ti.cal pre.sE1..tre of thJ.s syste:.11 is not as great a.s .might have A curve thru the cr.l. tica1. 110."nts ot.' both pro- pane and pentane, and thru the point of max.Lnu.;n temperatu:r·t: i'or- the EX.J..6tence of two phases in ;.1.Lxtui""eS 1 and 3 woul0. have defJ..:ned the locus oi' the cr.icondE:ntherm C'.m.ditions :for all Thl c curve could h ·,.ve bten shvvfn oz, Figure 5. In Ei.ither case it f'alJ.s below the critical curve, for· at a given co.t.1_;.i \Js.1. tion the. cr.Lcondentherm press,..ire i~ l,:;SS tl:;.a.n the cri- tical pressm•E. , ·,oJiilE. the temp E: r-.'.:lture, by de:f i n :.i. tJ.GllJ is higher than that at the crit1cal state. The cr ... co ndentLer·m da t :.i oi' Table .I. II 1.nd.icat~ that at COIUDOSition -" clof:.;e to €..t.tllE.r Dure A CO ,HDOH~mt.i ~ tb.E: c.L.i':fereL.ce betv,een tl1E: cr:i.. tical stateo and the cricondentherm ..1..s small, but th .it ,~t c •j:i1;)osi tionf. in the ne i 6 .hborhood. of :30 ;;iole percent p.ropane, the difference becomes cc:nsiderable, th€ max:...,nu.m two-phase tE:dnperature being abot:.1.t 7° higher t.tia n the critical te!rrper21 ture at this .v o int. CRITICAL LOCUS PRESSURE LB. PER SQ . IN . 275 175 375 TEMPERATURE / o Figure 6. F Bubble point pressure-Temperature curves for Mixtures 1, 2, and 3, showing vapor-pressure curves of propane and n-pentane. DATA Composition of Mi x tures : Mole percent propane Mol a percent n- pantane 5? . 80 62 . 20 55 . 57 44. 43 Mi xture l : M.1x t ur e 2: Mixtur e 5 : Pr essures in pounds per square i nch abaoluta at even s pec i fi c vol mnes . Mix tur e 1: 0 .o4, 0 . 048 0. 06 o.os 0 .10 130 104- . 8 1 03 . 3 101 . 4 98 . ? 95 . 3 l (> O 0 146 .7 144.9 1 42 . 5- 1 38 ,.l l ~S4 . 3 0 ; :~02 . i.~ 199.5 196.4 189 . 2 183. 9 220° 266 . 3 2ta. l }~54 . 0 24~.l 234 .6 0 341. 4 33b .O 3B b . 1~ !51 1. 7 29t1 . 6 42~~. 6 410 . 0 388. 0 366 .? 529 . 5 !)12 . 4 483 ,.l 453 . 8 560 . 0 5 89 . 0 Vol um.e t cu . rt . per Temper ~.1 ture , 0 1 90 ,36 0 0 28 0 310 330° 0 j'. 'OUn d · 0 1,p Mixture 2; Volume , cu . rt . per pouuct 0.04 0 . 05 0 . 06 130° }~ 37 . 0 2~6 . 0 236 . 2 160° 322 . 0 319 . 7 31? . 8 400 . 7 397 . 5 3Sr 4 . 9 210° 52 6 . 0 t:12 1. '9 . 571 . f} 565 . 0 11.'empero. ture • 180 0 .F 0 ·i 200 ,., Mixture 3 : 0 . 04 0.05 o.oo o. os 0. 10 130° lb4 . 3 lt ,;. 9 l ol . 3 148. 2 141'.> .9 lo0° El2.0 ::: 0 9. l zoo .a 201 . 6 197 . 2 190° 28t'> . 0 281 . ,1 27 7.'l 269 . ~; :ao2 . o " ';,00 .::,.., 371 . l 304 . 5 358 . 0 345 . 8 334.7 250° ~07 . ~ 465 . 2 454 . l 4;;7 • 0 419 . 8 583.7 bo9 . l 541 . 8 518 . l Volume . au . ft . per pt)UUd Temperature , ()tr 280° .1165 .otsoo .o::' sa4 .0362 . 0342 • {)865 . 0467 550 .1189 . 0685 .0413 500 .ltl4 .1025 .0418 .1839 330° .1371 .1734 310° 450 400 350 .0688 .1087 .0977 .0365 .0344 .0327 .0516 250 300 • 05€>6 . 0463 . 0328 280° • J 3l.6 250° 200 0 .0330 > 220 . 0 516 190° 150 160° .0696 130° 100 Pressure, lb. per sq. in. Temperature, O ,i'' Mixture 1: Specific volunes in cubio feet per pound et even pres s ures. 2 : .03723 .03698 .03679 .03510 . 03465 .034 50 • 0~4:18 .0342 7 .03200 .03251 - .03496 .03480 .03268 .03245 .03239 .03229 .03220 . 03214 350 400 450 500 550 500 650 700 .0;5645 .03657 .03752 . 0 352.8 .0.32HO 180° !300 0 160 • 05293 130° 250 Pressure, lb. _per s q . in . Ton1perature, 0 Jf Mixture 0 .04057 .04098 .04168 .04265 210 .. 04}165 .04349 .04492 220° .04588 .04821 230° 3: .03660 .05650 .03400 .03597 .05220 .03218 .05066 400 500 550 650 &00 .03640 .03685 .03410 .03227 .03072 350 450 .03421 .. 03238 .03080 300 .03436 .03248 .03710 220° .03087 .03453 0 190 250 ieo0 • 03093 0 130 200 Pressure, lb. per sq. in• Temperature, °F Ji.iixture .04880 .03924 . 03960 .04010 250° .04504 .04668 280° 148.3 160° 0 106.2 .0660 .07~2 593.9 508.0 330° 340° .0480 • 04:~ ::} 529.6 430.3, 310° 0 342.2 ..~;,oJ; 00 280 .03u4 268.7 220° .0388 .0346 .0330 .0317 204.2 190 Volume lb.per sq.in. au.rt.per lb. J):r-esaure 130° o !:? Temperature Mixture 1: 574.l 529 . B 210° 323.3 237.3 401.4 220° \Tolume .04610 .04523 . 037S2 . 035~9 • 03294 lb.per sq.in. cu.rt.per lb . Pressure .180° 160 0 uw0 OJf 'Temperature 111xture 2.: Bubble F·o1nt Gondi tions TABLE; II 280 0 <:)1';00 &;;.;/ 587.6 4?4.0 373.2 2 m J.l 190° 220° .03254 215.7 100° .04?32 .04055 .03?28 .0545.6 .03097 au.rt.per lb. 156.3 lb. per sq_.in. OF Volume 150° I' ressure Tm.11pera ture r,U xture 3: 182. ,, 246 . 6 0 3io0 280 309.? 241.l 180.3 133.2 250° 220 3?8.9 3-02.0 458.'7 370.9 !~90.5 231.7 1'75.3 229.9 156.9 100.1 irrn.4 l)0 .9 0.3 183.5 97.0 69 .0 0.2 69.l 4'7.8 0.1 138.7 64.l 41.8 :~o .5 0 94 .0 0 190° 160 0 1300 Tempers.ture, 0 :c- Composition, n1 551.0 448.1 35'1.7 536.2 4;, 1.4 337 . 9 259.9 215.9 ~l.O 192.2 l:59.4 0.5 158.6 ll.4.3 0.4 508.7 399.2 506.3 2;~e. 9 164.8 0.6 b93.6 463.l 354.8 262 .3 191.l 0 .1 Bubble point µressur~~ i.n pounds per square ineh a t even eomposi tions. 530.3 406.8 299.0 218.6 o.s 599.8 453.9 559.l 246.2 0.9 525.5 38!3.2 273 .5 1.0 II I 590. Crioondentherm: 344.2 . 0 340.2° * 0 * >f: 'l'empera t ure : Pressure 0.1 0 .2 o.:, 0.4 0.5 0.6 0.8 0 0.9 307.2° :102 e V ~ F o. l.O Temperature 3 ~B?.O 37H .5 368.0 36 0.0 3 41;.0 320.0 };98.0 :~?8.0 257 .0 2:12.0 ~06 .3 48 j .4 510 .6 540 .7 559.4 5 95.2 518.8 532.0 635 . 9 633.5 627.5 617.4 38'7 • 0 37?. 7 ~'166 . 0 ~)5;S. 3 338. 0 317 .2 l:9 6.5 275. 7 rrn 5.l 231. 3 206. 3 485.4 516.l 552 .0 584 .9 613.3 637.8 6bl .4 655 .0 650.8 637.0 617.4 0 Pressures in pounds Im r square inch absolute . Crieondentherra: 'I'empera ture, ? Fressure Critical: Composition, nl 0.7 627.8 048.7 . r . lb. per s,1.1n. o't. F r rcmsure 1Uxture Temperature l. Critica l nnd ,:ricundentherm cor1d1 t,i on s at ev,m compoei tions GOS . ~) Critical: 1 ·• ~ ... b.per sq. 111. Pressure Mixture Critical and Criconclentherm Data T;'~BLE RE.F'RHENCES Ind. ling. Cherri. _g§, 1218 - Young, J. Chem. Soc. ,'1 7 640 ( 1885) • :3. Bahlke and Kay , Ind . :Lr.g. Chem. ~, 2:~1 (1932). 4. Cummings, Ston es and Valante, Ibid . 5. Sage , Lacey and Schaaf'sma, Ibid. fil, 48 (1035). 6. Sage , Backus and Ver:neulent Ibid. g§, 489 (h,3o). 7. £Jell.is , 'Ib.esis , California Ins t.itute o:f TecL11olo.g-y, 1~38, gg, 7 28 (19~'.33). I wish to ex-jlrets iey- sincere a _p preciation to Dr. B. lh Sage and Dl»• Vi• Ih LaC&.f for the assistanc~ tll,E;y h ~iv6 &;iyen 1-ue in the preparation of this t.-hesis, and to tw • . Lee C~micha.el wto obtain€d much of the data h€r, reported• work of' Mr. e. w. Nyswander in d.e veloping the apparatus used.· has proved invaluable. Ii':i.na:neial a.ssi$tanee of' the AilHtriean Petroleum Institute made possible t.r.1ie research.