Fluid Phase Equilibria, 56 (1990) 39-57 Science Publishers B. ., !

"s#erda" - Prin#ed in $e %e#herlands

A non-cubic equation of state for and phase equilibrium calculations (pure compounds)
&i'r(i' S'a)e, Eniricerche *-+0,097 San -'na#' .ilanese, *#al/ Abstract: A new quartic van der Waals-type equation of state is proposed. The repulsive part is an extension of the original form, with a behaviour similar to that of the rigorous expression by but retaining its original simpli city. The a ractive part has the same form as in the classical cubic !"#. $orrelation of and vapour-pressure data proves that the new !"# is superior to the classical cubic equations. The laws of dependence of the parameters on temperature are simple and some general constraints can be so that the number of ad%ustable parameters can be reduced down to two only& they can be determined from one vapour pressure and one liquid density value and applied with confidence in a temperature range from the boiling point up to supercritical temperatures. With one more ad%ustable parameter, determined from an additional vapour pressure value, the application range can be extended down to the triple point. $ubic equations of state have found wide application for process design, especially calculations, as they o'er a good balance of simplicity and accuracy. Their wea( point is in general their low accuracy in calculations )which does not a'ect their good accuracy in calculations, due to an error between the two phases*. The need of a more accurate description of the behaviour of pure compounds and their mixtures becomes im portant in particular conditions, such as those found in supercritical fluid extraction.

Foreword Si"0le cubic ha)e been rendered s'0his#ica#ed b/ "an/ au#h'rs in 'rder #' ')erc'"e #ha# 1ea2 0'in#, bu# i# has bec'"e e)iden# #ha# #heir accurac/ cann'# (' be/'nd a cer#ain i# is en'u(h #' c'"0are #he )alues '3 #he cri#ical c'"0ressibili#/ (i)en b/ an/ cubic 1i#h #he e40eri"en#al 'nes5 #/0ical calcula#ed )alues are #'' hi(h b/ "'re #han 106 and such an err'r is "ain#ained ')er #he cri#ical area. 70 #' n'1 #he need 3'r "'re accura#e da#a has 3'und a s'lu#i'n in #he de)el'0"en# '3 accura#e bu# c'"0lica#ed equa#i'ns, 1i#h "an/ ad8us#able 0ara"e#ers, 1h'se de#er"ina#i'n requires #he a)ailabili#/ '3 0len#i3ul accura#e e40eri"en#al da#a, n'# a)ailable usuall/9 #heir a00lica#i'n is #hus res#ric#ed #' a hand3ul '3 1ell s#udied subs#ances. *# is s#ill desirable #' ha)e an equa#i'n '3 s#a#e 1i#h a li"i#ed nu"ber '3 0ara"e#ers and a be:er accurac/ #han i# can be a:ained b/ a cubic E;S. <e#, such an E;S c'uld n'# be e40ec#ed #' 0r')ide #he )er/ hi(h accuracies reached b/ #he "'re s0eciali=ed "ul#i-0ara"e#er equa#i'ns, accuracies 1hich are n'# necessar/ 3'r 0r'cess desi(n 0ur0'ses. $e 0r'0'sed equa#i'n '3 s#a#e is based 'n #he sa"e 0hil's'0h/ '3 all )an der >aals-#/0e equa#i'ns, i# includes #1' c'n#ribu#i'ns #' #he #'#al 0ressure5 a re0ulsi)e 'ne, c'nnec#ed #' #he ?ni#e )'lu"e and an a:rac#i)e 'ne e40ressin( #he "'lecular in#erac#i'ns.

Repulsive part *n #he classical #he re0ulsi)e e@ec# is e40ressed b/ a )er/ si"0le equa#i'n5 RT P re0 = (1) v b 'r P re0 v v b (1A) Z re0 = = =1 + RT v b v b 1hich is n'# in a(ree"en# 1i#h #he resul#s '3 c'"0u#er si"ula#i'ns '3 s/s#e"s 3'r"ed b/ ri(id s0heres. Such resul#s are "uch be:er re0resen#ed b/ a 1ell 2n'1n equa#i'n 0r'0'sed b/ Barnahan and S#arlin(5 + C y + y Z re0 = 1 + (+) 3 ( 1 y ) 1here y D b ECv . $e B-S equa#i'n has been a00lied b/ "an/ au#h'rs as a subs#i#u#e 3'r #he )d> e40ressi'n (1A). *#s "ain dra1bac2 is i#s anal/#ical c'"0le4i#/, 1hich "a2es #he s'lu#i'n '3 #he E;S and an/ anal/#ical "ani0ula#i'n "'re diFcul#. $e B-S e40ressi'n can be re0laced e@ec#i)el/ b/ "uch si"0ler 3'r"s. Sc': (1971) has 0r'0'sed5 Cy b Z re0 = 1 + = 1+ (3) 1 + y v b / + $e 3ac#'r + a# #he den'"ina#'r can be re0laced b/ 1.6, s' as #' ha)e #he sa"e )alues '3 Z E and 2Z E2 as #h'se (i)en b/ #he B-S equa#i'n, 3'r densi#/ #endin( #' =er'5

3G

G. Soave #he "'re (eneral 3'r"5

Table I.E40eri"en#al da#a used 3'r c'rrela#i'n B'"0'und ar('n ni#r'(en "e#hane e#h/lene e#hane 0r'0ane n-bu#ane ben=ene carb'n di'4ide h/dr'(en sul?de "e#h/l chl'ride #ricu'r'"e#hane a""'nia ace#'ne "e#han'l e#han'l T [\] N G6 6C 91 113 1+0 1C5 170 +GG +1G +G+ 175 1+5 +03 +59 +GG +93
Z re0 1 +

T [^_ P [\] N 300 C00 360 600 700 600 511 673 6+0 C93 C9G C53 760 53G 573 6+3 bar 0.GG 0.15 0.1+ 0.005 0.003 0.001b5 0.001b1 0.07Gb0 5.5 13.3 0.00G 0.00+ 0.11 0.0C+ 0.09G 0.05G

P [^_ bar 1000 1000 1000 3000 G00 +00 6G0 +G95 600 1706 30C +00 5000 300 690 690

-a#a s'urce (T ` T a) H1I H9I H10I H11I H1+I H1I H1I H13I H1I H+I H3I HCI H5I H6I H7I HGI

cb (5) vb 1here c is a 3ac#'r 1hich, in 0rinci0le, sh'uld increase 1i#h #he "'lecular di"ensi'ns, as 0'in#ed 'u# b/ >ils'n H1CI. Eq. (5) 1as selec#ed #' e40ress #he re0ulsi)e 0ar# '3 #he ne1 JKL !n/ decisi'n ab'u# #he )alue '3 c is dela/ed un#il a 3'r" '3 #he a:rac#i)e 0ar# has been selec#ed and #he 0er3'r"ance '3 #he ne1 JKL has been chec2ed. Z re0 = 1 +

(C) b v b / 1.6 Eqs. (1) #' (C) are c'"0ared in Fi(. 1 3'r )ari'us )alues '3 b Ev . *# is seen #ha# Eq.(C) is )er/ near #' Eq.(+) (B-S) a# #he l'1er densi#ies, 1hile Eq.(3), less accura#e a# l'1 densi#ies, is be:er a# #he hi(her 'nes. Eq.(1) (#he )d> e40ressi'n) di)er(es ra0idl/ and is ruled 'u#. Eqs. (3) and (C) can be c'nsidered as 0ar#icular cases '3 C

1 0 0.05 0.1 0.15 0.+ 0.+5

Fig. 1. Me0ulsi)e Z (Eqns. 1 #' C)

Atractive part *n 0ar# #he nu"er'us )an der >aals-#/0e equa#i'ns '3 s#a#e 0's0'ed in #he li#era#ure, #he a:ac#i)e e@ec#s '3 #he "'lecular in#erac#i'ns are e40ressed n )ari'us 3'r"s, 1hich can be c'llec#ed in#' a (eneral e40ressi'n5 a v Z a: = + (6) + v +u b v +w b 1here #he adi"en#i'nal 3ac#'rs u , w are ei#her assi(ned, 'r c'ns#rained, 'r 3reel/ ad8us#ed. $e ?rs# case is #ha# '3 #he s'-called #1'-0ara"e#er cubic equa#i'ns, includin( e.(. #he 'ri(ninal )d> JKL (u D w D 0), #he Medlich-N1'n( (OP) JKL and i#s "an/ )aria#i'ns (u D 1, v D 0) and #he Pen(-M'bins'n (QO) JKL (u D +, w D R1). !ll #h'se equa#i'ns c'n#ain #1' 0ara"e#ers 'nl/, 1h'se )alues (a# leas#, #heir )alues a# #he cri#ical #e"0era#ue) can be (and are usuall/) de#er"ined b/ i"0'sin( #he cri#ical c'ns#rain#s. $e/ are s' ?4ed de?ni#el/ and ha)e #he sa"e )alues 3'r all c'"0'unds, 1hich is a seri'us li"i#a#i'n, in 0ar#icular 3'r QST calcula#i'ns, since i# can be sh'1n easil/ #ha# #he cri#ical is'#her"s ha)e a di@eren# 3'r" 3r'" subs#ance #' subs#ance. ! sec'nd #/0e '3 JKL 3r'" #he li#era#ure (Sch"id#, >en=el H15I9 Uar"enss V Nna00 H16I9 Pa#el V We8a H17I), al#h'u(h 1ri:en in di@eren# 1a/s, can be c'llec#ed in#' a sin(le 3'r", 1i#h 'ne "'re 0ara"e#er 1hich is leX 3ree b/ #he cri#ical c'ns#rain#s, and 'be/in( #he c'ndi#i'n5 u Y w D l. Such c'ns#rain# has n' #he're#ical 8us#i?ca#i'n, bu# in 3ac# a 3-0ara"e#er JKL '3 #ha# #/0e is al"'s# as (''d as a C-0ara"e#er 'ne, as i# 1ill be sh'1n 3ur#her 'n. $e c'rrela#i'n '3 0ure-c'"0'nen# PVT and )a0'r-0ressure da#a /ield al1a/s )alues '3 u ,w such as #' (i)e a 0'si#i)e discri"inan# (u + Z C w ) b +5 #he quadra#ic e40ressi'n a# #he den'"ina#'r '3 #he a:rac#i)e 0ar# '3 Eq.(6) has #hus al1a/s real r''#s and can be re0laced, 1i#h'u# an/ real li"i#a#i'ns, b/ a 0r'duc# '3 #1' bin'"ials, 1hich has #he ad)an#a(e '3 enablin( an easier anal/#ical #rea#"en#5 a v Z a: = (6A) ( v + d )( v + e ) $e ne1 equa#i'n '3 s#a#e has #hen #he 3'll'1in( 3'r"5 cb av Z = 1+ (7) v b ( v + d )( v + e ) Eq. (7) is '3 3'ur#h de(ree in (eneral (e4ce0#in( #he cases 1i#h c D 1 'r e D 0) and has + 'r C real r''#s (a# su0er- 'r subcri#ical #e"0era#ures, res0ec#i)el/), 'ne '3 1hich 'u#side #he all'1able ran(e 3r'" =er' densi#/ #' 1Eb .

G. Soave 7nli2e cubic JKLA s, n' direc# s'lu#i'n 0r'cedure is a)ailable9 #his is a dra1bac2, bu# 'nl/ 1i#h a n'n-cubic JKL a real i"0r')e"en# can be 'b#ained, as i# 1ill be sh'1n 3ur#her 'n. *n 0ar#icular, a s#r'n(l/ ne(a#i)e (and e)en, near #' Zb ) )alue '3 #he 0ara"e#er e is essen#ial 3'r a (''d beha)i'r a# #he hi(her densi#ies. !s an indirec# 0r''3, i3 #he a:rac#i)e 0ar# 1ere ("'re c'""'nl/ bu# n' less e"0iricall/) e40ressed b/ a series '3 densi#/ 0'1ers, hi(h 0'1ers 1'uld be required #' e40ress #he s#r'n( de0endence '3 0ressure 'n densi#/, a# hi(h )alues '3 #he la:er. .'re si"0l/, #his is e40ressed b/ Eq.(6A) 1i#h s#r'n(l/ ne(a#i)e )alues '3 e . $e Pen(-M'bins'n JKL, 1hich is clai"ed #' be 0ar#icularl/ sui#ed 3'r QST calcula#i'ns, has in 3ac# a ne(a#i)e1alue '3 e 9 un3'r#una#el/, #1' 0ara"e#ers 'nl/ (b'#h de?ned b/ #he cri#ical c'ns#rain#s) are #'' 3e1 3'r a reall/ sa#is3ac#'r/ JKL. Experimental data W1' 2inds '3 da#a "us# be c'nsidered in 'rder #' de)el'0 an JKL 1i#h a (eneral a00lica#i'n5 )a0'ur-0ressure da#a9 an accura#e descri0#i'n '3 0urec'"0'und )a0'ur 0ressures is a )er/ s#ric# cri#eri'n and is essen#ial 3'r a 3ur#her a00lica#i'n #' "ul#i-c'"0'nen# 0hase equilibria. E40eri"en#al )a0'ur 0ressure da#a can be re0laced b/ )alues (enera#ed b/ sui#able e40ressi'ns, such as #he C-0ara"e#er >a(ner equa#i'n5 P 1.5 3 6 ln = a 1 ( 1 T r )+ a + ( 1 T r ) + a 3 ( 1 T r ) + a C ( 1 T r ) Pc 3'r 1hich an e4haus#i)e c'"0ila#i'n '3 c'ns#an#s has been (i)en b/ .c&arr/ H1GI and la#er resu"ed and enhanced b/ Table II.c )alues 3r'" unc'ns#rained c'rrela#i'n B'"0'und %'.P#s. ar('n 90 ni#r'(en GC "e#hane GC e#h/lene G+ e#hane G0 0r'0ane 91 n-bu#ane 75 ben=ene 51 carb'n di'4ide 100 h/dr'(en sul?de 7G "e#h/lchl'ride GG cu'r'3'r" G0 a""'nia 100 ace#'ne ++ "e#han'l1 C7 e#han'l 63
1

39

Meid et al . H19I. PVT da#a. Par#icularl/ cri#ical are #he liquid densi#/ )alues, 1hich a@ec# "'s# #he 0ara"e#er )alues9 e40eri"en#al da#a can be re0laced b/ )alues (enera#ed b/ #he accura#e Mac2e: equa#i'n5 R T c 1+ (1 T )+/ 7 vd Z (G) sa# = P c Ma 1h'se 0ara"e#ers can be 3'und in a c'"0ila#i'n b/ S0encer and !dler H+0I. PVT da#a a# su0ercri#ical #e"0era#ures are n'# 0len#i3ul in #he li#era#ure9 in s'"e cases #heir )alues can be (enera#ed b/ )er/ accura#e (and c'"0le4) equa#i'ns '3 s#a#e, 1h'se 0ara"e#ers are a)ailable 3'r a 3e1 c'"0'unds.
r

c 1.69C 1.6G+ 1.700 1.G1C 1.736 1.630 1.55G 1.5+1 1.716 1.C50 1.109 0.96C 1.+G5 1.33C 1.C66 1.6C3 O.m.L.

jP k, jl

1.1 1.0 0.9 1.3 1.3 1.6 +.0 3.+ 1.7 1.9 1.9 1.9 1.7 1.C +.9 1.6 1.G

Parameter dependence on temperature B/ unc'ns#rained c'rrela#i'n '3 sin(le-#e"0era#ure da#a, #he 'b#ained 0ara"e#er )alues e4hibi#ed an erra#ic #rend, due #' b'#h #he inaccurac/ '3 #he da#a and #he inadequac/ '3 #he "'del9 such erra#ic beha)i'ur is 0ar#icularl/ e)iden# near #he cri#ical #e"0era#ure and 3'r #h'se 0ara"e#ers (li2e c ) ha)in( a s"aller incuence 'n resul#s. %e)er#heless s'"e c'ns#an# beha)i'urs can be iden#i?ed, n'# de0endin( 'n #he 0ar#icular c'"0'und e4a"ined5 a) e D b P cER T c is al"'s# c'ns#an# 1i#h #he #e"0era#ure9 i3 leX #' )ar/, #he resul#s 1'uld be li:le i"0r')ed and 'ne "'re ad8us#able 0ara"e#er 1'uld ha)e #' be de#er"ined, i# 1as s' assu"ed as c'ns#an#5 e = ec (9) b) f D a P cER T c and g D d P cER T c decrease 1i#h increasin( #he #e"0era#ure and a #endenc/ is qui#e e)iden# 3'r b'#h #' (' #' =er' 3'r T #endin( #' in?ni#/ (1hich, 3'r a, is 0h/sicall/ "eanin(3ul). F'r g, a 0ara"e#er 1i#h s"all incuence 'n resul#s, a si"0le in)erse la1 can be assu"ed5 gc g= (10) Tr 1hile 3'r f a "'re ce4ible e40ressi'n 1as used, 1i#h #1' ad8us#able c'eFcien#s5 f = fc h ( T r ) (11) (1+) Tr c) i D e P cER T c is al"'s# c'ns#an# and a00r'aches #he )alue Re9 al#h'u(h i# a@ec#s resul#s c'nsiderabl/, "ainl/ a# hi(h densi#ies, i# is diFcul# #' de?ne an e40ressi'n 3'r i#, #hus 3'r #he sa2e '3 si"0lici#/ i# 1as assu"ed as c'ns#an#5 i = ic (13) Basin( 'n #he ab')e c'nclusi'ns and assu"0#i'ns, #he ?nal 3'r" '3 #he ne1 equa#i'n '3 s#a#e 3'r a 0ure c'"0'und is5 ac h ( T r ) v Pv b Z= =1 + c (1C) RT v b ( v +d c / T r )( v + e ) 'r x Pr fc h ( T r ) x e Z= = 1+ c (15) Tr x e ( x + g c / T r )( v + i ) 1here5
h ( T r )= 1 + ( 1 T r ) m +

n Tr

n' liquid densi#/ da#a used.

C0
x =v Pc R Tc

G. Soave (16) cludin( C in'r(anic (ases (!r, %n, B;n, UnS), 6 h/dr'carb'ns 3r'" "e#hane #' ben=ene, C 0'lar, n'n-ass'cia#in( c'"0'unds (BUoBl, BUFo, %Uo, ace#'ne) and + alc'h'ls ("e#han'l and e#han'l). $e #/0es '3 c'"0'unds and #he c'ndi#i'n ran(es are 1ell re0resen#a#i)e. F'r #he alc'h'ls n' liquid 0hase densi#/ da#a 1ere used, since #he 'ccurrin( '3 s#r'n( ass'cia#i'n 0hen'"ena "a2es #he" "isleadin(. $e ab')e da#a 1ere c'rrela#ed #' de#er"ine #he E;S 0ara"e#ers '3 each c'"0'und, 1i#h 'r 1i#h'u# a00lica#i'n '3 )ari'us c'ns#rain#s. $e 'b8ec#i)e 3unc#i'n #' be "ini"i=ed 1as5 + Z calc + 1 +100 (ln hd ln h ) Z e40 1here b'#h Z a^pa and Z q_r and #he 3u(aci#/ c'eFcien#s h 1ere e)alua#ed a# #he e40eri"en#al #e"0era#ures and 0ressures. $e di@erence (ln hd R ln h ) 1as assu"ed 3'r #he sa2e '3 si"0lici#/ as an a00r'4i"a#i'n '3 #he "'re ri('r'us rela#i)e err'r 'n )a0'r 0ressure9 #he di@erence is s"all and #he i#era#i)e calcula#i'n '3 )a0'ur 0ressure c'uld #hus be a)'ided. $e resul#s '3 #he ?rs# unc'ns#rained c'rrela#i'ns (bu# a00l/in( #he cri#ical c'ns#rain#s) are re0'r#ed in Wab. **, 1here #he jP k, jl #er" is #he ?nal ')erall OmL err'r5

ritical constraints *"0'sin( #he cri#ical c'ns#rain#s, i.e. 3'rcin( #he ?rs# and sec'nd deri)a#i)es '3 0ressure 1i#h )'lu"e #' be =er' a# #he cri#ical 0'in#, besides bein( #he're#icall/ c'rrec#, has a d'uble ad)an#a(e5 ?rs#, i# decreases #he nu"ber '3 ad8us#able 0ara"e#ers b/ re0lacin( #1' '3 #he" 1i#h #he cri#ical c'ns#an#s T c, P c, 1hich are 'Xen 2n'1n9 sec'nd, i# ensures a c'rrec# beha)i'ur in #he )icini#ies '3 #he cri#ical 0'in# (ne(lec#in(, 'b)i'usl/, #he n'n-anal/#ic e@ec#s in #he i""edia#e surr'undin(s '3 i#). Since #he 0ara"e#er )alues 1ere 1ri:en as 3rac#i'ns '3 #he 3ac#'r (R T cEP c), i# is c'n)enien# #' re0lace #he cri#ical )'lu"e v a b/ Z a(R T aEP a)9 #he e4#ra 0ara"e#er Z c is de?ned b/ Eq. (7) as a 3unc#i'n '3 #he '#her 'nes. >e ha)e #hus (a# #he cri#ical #e"0era#ure) 6 0ara"e#ers fc, e, c, gc, i, Z c, 3 '3 1hich (sa/ fc, gc, i) are de?ned #hr'u(h Eq. (7) and #he cri#ical c'ns#rain#s. !nal/#ical de#ails are (i)en in #he !00endi4 . !ata correlation " first results $e s#ra#e(/ 3'll'1ed here 1as #' add a)ailable hi(h #e"0era#ure da#a #' an equal nu"ber '3 )a0'ur-0ressure and sa#ura#ed-liquid densi#/ da#a, 1hich 1ere (enera#ed b/ #he >a(ner and Mac2e: equa#i'ns res0ec#i)el/, 1i#h 0ara"e#ers 3r'" #he li#era#ure (Meid et al . H19I). B'"0'unds e4a"ined, #e"0era#ure and 0ressure ran(es and da#a s'urces are re0'r#ed in Wab. *. -a#a 1ere a)ailable 3'r a #'#al '3 16 c'"0'unds, in-

100

er/ l'1 residual err'rs 1ere 'b#ained in all cases, re(ardless '3 #he na#ure '3 #he c'"0'und (0'lar 'r n'#)9 #his 1as a ?rs# c'n?r"a#i'n '3 #he s'undness '3 #he ne1 equa#i'n. $e )alues 'b#ained '3 #he 0ara"e#er c 1ere qui#e erra#ic, 1i#h n' e)iden# c'nnec#i'n #' #he na#ure 'r "'lecu-

[ (

jP k + Pk

+ /( + n ). ) + ( jl l ) ]

Table III. Mesul#s 3r'" c'rrela#i'ns 1i#h c D 1.6 (ad8us#able 0ara"e#ers5 e, Z a, m , n ) B'"0'und ar('n ni#r'(en "e#hane e#h/lene e#hane 0r'0ane n-bu#ane ben=ene carb'n di'4ide h/dr'(en sul?de "e#h/l chl'ride #ricu'r'"e#hane a""'nia ace#'ne "e#han'l1 e#han'l
1

e 0.095b0 0.093bG 0.09+b0 0.0GCb+ 0.0GCb9 0.0G7b1 0.0G6b5 0.0GCb7 0.0G7bC 0.096b6 0.0GCb3 0.076b5 0.06GbC 0.071b7 0.05Gb9 0.0G1b0

Za 0.306b9 0.307b3 0.306b5 0.310b+ 0.30GbC 0.301b0 0.+9Gb3 0.+96b6 0.+99b+ 0.+97bG 0.+G9b1 0.+G7b7 0.+79b7 0.+75b3 0.+51b5 0.+60b0

m 0.39GbG 0.CC9b7 0.CC7b0 0.5G1b1 0.599bC 0.605b5 0.639b0 0.63+b6 0.65CbC 0.CC+b5 0.57Gb5 0.765b9 0.79Gb7 0.7G5b1 1.095b0 0.77Cb6

n 0.0+5 0.0+G 0.011b9 0.00Gb5 0.001b3 0.01Cb3 0.0+0b+ 0.037b+ 0.0++b6 0.036b+ 0.0+0b+ 0.037b+ 0.0++b6 0.036b+ R0.051 0.035b9

ga +.33 +.33 +.3G +.3C +.39 +.60 +.69 +.77 +.65 +.53 3.00 3.+C 3.79 3.G+ 5.CC 3.G5

iEe R0.GG R0.G7 R0.G6 R0.77 R0.G0 R0.G6 R0.G7 R0.G7 R0.G7 R0.9+ R0.90 R0.G6 R0.GC R0.90 R0.93 R0.9G

uYw R0.59 R0.56 R0.53 R0.+C R0.30 R0.50 R0.5+ R0.50 R0.53 R0.7+ R0.60 R0.C1 R0.+C R0.50 R0.57 R0.9+ O.m.L.

j,6 1.1 1.1 1.0 1.5 1.C 1.6 +.0 3.+ 1.7 +.0 +.0 +.1 +.1 1.6 3.C 1.3 1.9

%' liquid densi#/ da#a used.

G. Soave lar di"ensi'ns '3 #he c'"0'unds9 all hi(her #han uni#/ and (r'u0ed a00aren#l/ ar'und #ha# )alue 1.6 1hich 1as sh'1n #' 3'rce #he a(ree"en# '3 #he re0ulsi)e 0ar# '3 #he JKL 1i#h #he B-S e40ressi'n a# l'1 densi#ies. $is is in c'n#ras# 1i#h #he c'nclusi'ns '3 >ils'n, acc'rdin( #' 1h'" i# sh'uld increase 1i#h #he "'lecular di"ensi'ns, s#ar#in( 3r'" a )alue +9 such beha)i'ur 1as n'# 3'und and c'uld be due #' an inedaqua#e a:rac#i)e 0ar# '3 #he JKL. Reducin# the number of ad$ustable parameters Wab. *** sh'1s #he resul#s '3 a ne1 c'rrela#i'n 1i#h c ?4ed a# a )alue 1.6 (C ad8us#able 0ara"e#ers5 e, Z a, m , n )5 #he err'rs 1ere 0rac#icall/ #he sa"e as #h'se 1i#h c ad8us#ed #' #he bes# )alue, a 0r''3 '3 i#s "in'r i"0'r#ance. ! 3ur#her reduc#i'n in #he nu"ber '3 3ree 0ara"e#ers c'uld be necessar/ 1hen #he a)ailable da#a are )er/ li"i#ed 'r 1hen #he da#a #he"sel)es are '3 0''r quali#/, #' 0re)en# #he 0ara"e#ers 3r'" assu"in( unrealis#ic )alues. Fr'" #he )alues '3 #he 0ara"e#ers and '3 s'"e deri)ed 3ac#'rs re0'r#ed in Wab. ***, #he 3'll'1in( c'nclusi'ns can

C1

be dra1n5 $e resul#s are )er/ sensi#i)e #' #he )alue '3 e, #ha# cann'# be es#i"a#ed a priori and "us# be #rea#ed as ad8us#able. $e ra#i' gEe )aries "ar2edl/, assu"in( hi(h )alues 3'r 0'lar c'"0'unds. E)en i3 i# a@ec# li:le #he resul#s, i#s s0read n'# all'1 #' assu"e a c'ns#an# )alue 3'r all c'"0'unds. $e ra#i' iEe )aries 1i#hin a narr'1 ran(e9 /e# #his 0ara"e#er has a s#r'n( incuence 'n resul#s and cann'# be #rea#ed as a uni)ersal c'ns#an#. $e )alues '3 u D (ga Y i)Ee and w D ga iEes )ar/ se0ara#el/ ')er 1ide ran(es, bu# #heir su" re"ains rela#i)el/ c'ns#an#9 since i# has a s"all incuence 'n resul#s, i# can be ?4ed a# a c'ns#an# )alue5 (g + i ) gc u +w= c + + =0.5 (17) e e $e !00endi4 (i)es #he (i#era#i)e) calcula#i'n 0r'cedure #' de#er"ine Z a, in 0resence '3 #ha# c'ns#rain#. >i#h #he ab')e assu"0#i'n, #he ad8us#able 0ara"e#ers leX

Table IV.M''# "ean square j P sa# , jl 1i#h )ari'us assu"0#i'ns5 case a5 b5 c5 d5 e5 35 (5 h5 i5 c c c c c c c c c D 1, ga D e, i D 0 (Medlich-N1'n() D 1, ga D +.C1C e, i D R0.C1C e (Pen(-M'bins'n) D 1, i D 0 D 1, u Y w D 1 (3-0ara"e#er e'sAs 3r'" li#era#ure) D 1, g D ga D i ()an der >aals Y Penel'u4 )'lu"e shiX) D 1, n' c'ns#rain# D 1.6, n' c'ns#rain# (see Wab. * ) D 1.6, u Y w D R0.5 D 1.6, i D 0 c 3.0 3.0 3.C 3.C C.+ 3.G 3.7 C.3 5.5 3.0 C.6 +.9 3.C 3.6 3.C 5.3 5.0 C.0 d 3.0 +.7 3.3 3.3 3.9 3.C 3.+ 3.6 C.6 +7.0 C.1 +.0 1.9 +.0 1.9 3.C 3.5 3.+ e 3.0 +.9 3.+ +.9 3.7 3.7 3.5 C.+ 5.3 +.G C.7 C.G C.1 C.+ 5.0 6.7 5.G C.3 3 C.0 +.5 +.6 +.6 3.+ +.9 +.5 +.9 3.9 +.6 +.5 1.9 1.9 +.0 1.9 C.9 tu (+.9)+ ( C.0 1.1 1.0 1.0 1.5 1.C 1.6 +.0 3.+ 1.7 +.0 +.0 +.1 +.1 1.6 3.C 3.0 1.9 h 3.0 1.1 1.0 1.0 1.C 1.C 1.6 +.0 3.+ 1.7 +.3 1.G +.+ +.3 1.6 3.C +.G +.1 i 3.0 +.9 3.3 3.3 C.1 C.0 C.5 5.+ 6.1 3.0 C.9 C.3 5.1 C.C C.5 5.G 5.6 C.5

Base5 a b n'.0ara". + + ar('n 3.G 5.C ni#r'(en C.1 5.G "e#hane C.1 5.G e#h/lene 5.3 5.+ e#hane 5.C C.+ 0r'0ane 6.+ 3.+ n-bu#ane 7.7 3.6 ben=ene 9.5 C.6 h/dr'(en sul?de 7.5 +.7 "e#h/l chl'ride 6.G C.9 #ricu'r'"e#hane 10.9 3.+ #ricu'r'"e#hane 1C.1 6.0 a""'nia 1G.6 10.0 ace#'ne +5.0 13.6 "e#han'l1 3+.C ++.3 e#han'l +1.6 1+.0 O.m.L.5 1C.1 G.6 1 %' liquid densi#/ da#a used + usin( 3'r e#han'l #he err'r in c'l. d.

C+

G. Soave c'ns#rain#s (case (, C 0ara"e#ers), #he bes# ')erall. $e case i, 1i#h c D 1.6 and i D 0 (a cubic JKL 0r'0'sed b/ W'chi(i et al . H+1I), is a(ain a 0r''3 #ha# a ne(a#i)e )alue '3 i is essen#ial 3'r a real i"0r')e"en#. !s a ?nal c'nclusi'n, #he bes# resul#s 1ere 'b#ained 1hen #he 0ara"e#er c 1as leX 3ree #' assu"e ne(a#i)e )alues and 1i#h )alues '3 c di@eren# 3r'" #he uni#/ (i.e. 1i#h n'n-cubic JKLAs)9 in 0ar#icular a )alue c D 1.6 l''2s #' be #he bes# uni)ersal )alue. &sin# limited' low-temperature data *# "a/ ha00en #ha# 3'r cer#ain subs#ances )er/ li:le in3'r"a#i'n is a)ailable. diquid densi#/ da#a are 'Xen a)ailable ('r can be "easured easil/ an/1a/), es0eciall/ bel'1 #he b'ilin( 0'in#. $is 'ne is (enerall/ 2n'1n, 1hile '#her )a0'r 0ressure da#a are n'# al1a/s a)ailable and "a/ n'# be "easurable ')er a cer#ain #e"0era#ure, 3'r #he 'ccurrence '3 dec'"0'si#i'n 0hen'"ena. !s #' #he cri#ical c'ns#an#s, in #he case #he/ are n'# a)ailable 'r cann'# be "easured (0ar#icularl/ 3'r hea)/ subs#ances) #he cri#ical #e"0era#ure can be es#i"a#ed 1i#h suFcien# accurac/ b/ se)eral 0r'cedures, 1hile a c'nsis#en# )alue '3 #he cri#ical 0ressure can be 'b#ained b/ c'rrela#in( a# leas# #1' liquid-densi#/ )alues 1i#h #he Mac2e: equa#i'n, as 0r'0'sed b/ e#ere H++I. $e leas# a)ailable da#a are PVT da#a a# su0ercri#ical #e"0era#ures. $is (i)es rise #' #he ques#i'n 1he#her 0ara-

are 3 'nl/, i.e. e and #he c'eFcien#s m , n '3 h(T v) (Eq. 1+). $e )alues '3 #he c'eFcien# n '3 h(T v) are al1a/s s"all, b'#h 3'r 0'lar and n'n-0'lar c'"0'unds. de:in( n D 0 all'1s a (''d re0r'duc#i'n '3 e40eri"en#al )a0'ur 0ressures in a "'re li"i#ed ran(e (sa/, 3r'" 0.1 bars #' P a) and 1'uld reduce #he nu"ber '3 ad8us#able 0ara"e#ers #' + 'nl/. Such assu"0#i'n c'uld be ad'0#ed 1i#h a )er/ li"i#ed nu"ber '3 e40eri"en#al da#a, as i# 1ill be sh'1n 3ur#her 'n. omparin# the di%erent assumptions Wab. * re0'r#s #he resul#s 'b#ained 1i#h )ari'us assu"0#i'ns. S'"e s0eci?c c'nclusi'ns can be dra1n5 >i#h #1'-0ara"e#er equa#i'ns '3 s#a#e (M-N and P-M, cases a , b res0ec#i)el/), #he resul#s 1ere acce0#able 'nl/ 3'r li(h#, n'n 0'lar subs#ances. *n #he '#her cases, be:er resul#s 1ere 'b#ained in (eneral 1i#h c D 1.6 #han 1i#h c D 1. >i#h c D 1 (cubic JKLAs) #he resul#s 'b#ained 1i#h #he c'ns#rain# u Y w D 1 (case d) 1ere 'nl/ sli(h#l/ 1'rse #han 1i#h'u# c'ns#rain#s (case 3). $e case '3 #he )an der >aals JKL 1i#h a )'lu"e #ransla#i'n acc'rdin( #' Penel'u4 (case e) (a)e 1'rse resul#s #han 1i#h #he '#her 3-0ara"e#er 3'r"s. >i#h c D 1.6 and #he c'ns#rain# u Y w D R0.5 (case h, 3 0ara"e#ers) #he resul#s 1ere al"'s# #he sa"e #han 1i#h'u#

Table V.Para"e#er )alues 3r'" #he a#"'s0heric b'ilin( 0'in#, T w, and #he sa#ura#ed liquid densi#/ a# T w. !00lica#i'n #' #he calcula#i'n '3 )a0'r 0ressures and liquid densi#ies a# T w #' 0.9 T a and (as densi#ies a# T ` T a. case (a)5 c D 1.6, u Y w D R0.5, n D 0 case (b)5 c D 1, u Y w D 1, n D 0 (a) T x Ta T w, N jP sa# ar('n G7.3 0.7 ni#r'(en 77.C 0.5 "e#hane 111.6 0.C e#h/lene 169.3 1.0 e#hane 1GC.6 0.5 0r'0ane +31.1 0.3 n -bu#ane +7+.7 0.3 ben=ene 353.+ 0.9 carb'n di'4ide +1G.1 0.3 h/dr'(en sul?de +G+.0 0.1 "e#h/l chl'ride +C9.1 0.C #ricu'r'"e#hane 191.0 0.C a""'nia +39.G 0.3 ace#'ne 3+9.+ 0.3 O.m.L. 0.5 l'1er #e"0era#ure li"i# 3'r liquid densi#/ da#a jly 1.3 1.3 1.3 1.1 1.1 1.0 1.0 1.0 1.+ 1.5 1.+ 1.1 1.7 1.+ 1.+ T ` Ta jlz 1.3 1.1 1.1 1.6 1.5 1.6 +.C C.5 +.1 6.+ +.C +.9 3.1 +.5 +.G T x Ta jP sa# +.1 1.7 +.1 1.0 1.5 1.+ 0.9 0.9 0.+ 0.5 1.1 0.C 0.G 0.6 1.+ jly 5.0 C.7 C.G C.0 C.1 3.7 3.C +.G 3.3 3.3 3.+ +.C 1.6 1.6 3.6 (b) T ` Ta jlz 3.5 C.G C.C 5.1 C.3 3.1 C.6 6.5 3.1 7.+ 1.G +.6 +.3 +.C C.3

G. Soave "e#er )alues deri)ed 3r'" da#a ()a0'r 0ressures and liquid densi#ies) a# subcri#ical #e"0era#ures "a/ be used a# hi(h #e"0era#ures als'. F'r #ha# reas'n a #rial 1as d'ne, 1here 'nl/ #1' da#a 1ere used #' de#er"ine #he E;S 0ara"e#ers5 #he a#"'s0heric b'ilin( 0'in# t w and #he sa#ura#ed liquid densi#/ a# t w. *n 'rder #' reduce #he nu"ber '3 ad8us#able 0ara"e#ers #' + 'nl/, #he 3'll'1in( assu"0#i'ns 1ere "ade5 c D 1.6, n D 0 and u Y w D R0.5. F'r #he sa2e '3 c'"0aris'n, als' #he case 1i#h c D 1, u Y w D 1 and n D 0 1as c'nsidered. Subsequen#l/, #he )alues '3 #he 0ara"e#ers s' de#er"ined 1ere a00lied #' all PVT da#a a)ailable a# su0ercri#ical #e"0era#ures and #' )a0'ur 0ressure and liquid densi#/ )alues (enera#ed in #he #e"0era#ure ran(e 3r'" #he b'ilin( 0'in# #' 0.9 #i"es #he cri#ical #e"0era#ure. $is da#a se# is #/0ical '3 #he c'ndi#i'ns in)'l)ed in a su0ercri#ical e4#rac#i'n 0r'cess. $e resul#s are sh'1n in Wab. . >i#h c D 1.6 and #he c'ns#rain# u Y w D R0.5, )a0'ur 0ressures and liquid densi#ies 1ere re0r'duced 1ell ')er all #he ran(e, 1hile hi(h-#e"0era#ure da#a 1ere re0r'duced 1i#h al"'s# #he sa"e accurac/ #han #ha# b/ direc# c'rrela#i'n '3 #he 1h'le da#a se#s (c3r. Wab. * , case h, c')erin( #' a 1ider ran(e, bu# 1i#h 'ne "'re ad8us#able 0ara"e#er)9 #his is a c'n?r"a#i'n '3 #he c'nsis#enc/ '3 #he 0r'0'sed JKL. $e (eneral cubic JKL 1i#h c D 1, u Y w D 1 and n D 0 (a)e hi(her err'rs in all cases, in 0ar#icular 3'r #he liquid densi#/ near #he cri#ical #e"0era#ure and, a"a=in(l/, n'n0'lar c'"0'unds. $'se resul#s rule 'u# de?ni#el/ #ha# al#erna#e, 1hich c'uld s#ill l''2 a:rac#i)e 3'r i#s (rea#er si"0lici#/. $e ab')e 0r'cedure 1as n'# a00lied #' #he alc'h'ls, 1h'se densi#/ da#a can be "isleadin(, due #' #he 'ccurrin( '3 ass'cia#i'n 0hen'"ena. $e 0ara"e#ers de#er"ined b/ #he ab')e 0r'cedure cann'# be a00lied bel'1 #he a#"'s0heric b'ilin( #e"0era#ure, since calcula#ed )a0'ur 0ressures 1'uld di)er(e ra0idl/. *# c'uld be sh'1n h'1e)er #ha#, b/ in#r'duc#i'n '3 a sec'nd ad8us#able 0ara"e#er n , )a0'ur 0ressure and liquid densi#/ da#a c'uld be re0r'duced accura#el/ d'1n #' #he #ri0le 0'in#. !s a #/0ical. e4a"0le, #he )alues '3 e, m , n 1ere de#er"ined 3'r e#hane 3r'" i#s a#"'s0heric b'ilin( 0'in#, #he liquid densi#/ a# #he sa"e #e"0era#ure and #he )a0'ur 0ressure a# #he #ri0le 0'in# (90.C N, P {^| D 1.1C5}10~ bars)9 b/ a00l/in( #he 0ara"e#ers s' de#er"ined #' a da#a se# (enera#ed ')er a #e"0era#ure ran(e 3r'" #he #ru0le 0'in# #' 0.9 Ta, #he OmL 1ere 1.G6 3'r )a0'ur 0ressure and +.C6 3'r liquid densi#ies. Appendix Application of the critical constraints de# us 1ri#e Eq. 7 as v a v v Z = 1 +c 1 v b d e v + d v + e 1hence5 P 1 1 1 a 1 1 = +c RT v v b v d e v + d v + e 1 P 1 1 1 = +c + + R T v T v + (v b ) v

C3

(!.+)

( )
+

a 1 1 d e ( v + d )+ ( v +e )+

] ]

(!.3)

(!.1)

1 P 1 1 1 = +c 3 3 + R T v + T v 3 ( v b ) v (!.C) a 1 1 d e ( v + d )3 ( v +e )3 de:in( n'15 ac P c fc = RTc P cb e= RTc Pc dc gc = R Tc Pc e i= R Tc P cvc Z c= RTc and ac fc A= = (!.5) d c e gc i vc Zc B= = (!.6) v c b Z c e vc Zc = = (!.7) vc d c Z c + gc vc Zc != = (!.G) v c e Z c + i Eqs. !.1, !.3 and !.C are 1ri:en 1 + c ( B 1) A ( ! )= Z c + + + 1 +c ( B 1) A ( ! )=0 3 3 3 1 +c ( B 1) A ( ! )=0 de:in( n'1, 3'r #he sa2e '3 si"0lici#/5 1= 1 +c ( B 1) Z c (!.9) + (!.10) + = 1 +c ( B 1) 3 (!.11) 3= 1 + c ( B 1) 1e ha)e 1 + 3 A= = + (!.1+) += 3 3 ! ! ! 1hence5 + ( + ! )= (!.13) 1 + + 3 ( ! )= (!.1C) 1 1 ;nce #he su" and #he 0r'duc# '3 and ! are 2n'1n, #he/ can be 'b#ained as #he r''#s '3 #he equa#i'n5 + y y ( + ! )+( ! )= 0 i.e.5

( )

( ) ( )

CC

G. Soave an'l a# ele)a#ed #e"0era#ures and 0ressures, Bhe". En(. Pr'(. S/"0. Ser. 66 (1970) 11Z15. HGI U.<. d', d.*. S#iel, P W Beha)i'r '3 E#h/l !lc'h'l a# Ele)a#ed Pressures and We"0era#ures, *nd. En(. Bhe". Funda". G (1969) 713Z71G. H9I . . S/che), W.B. Sel')er, $er"'d/na"ic Pr'0er#ies ;3 %i#r'(en (%a#i'nal S#andard Me3erence -a#a Ser)ice '3 #he 7SSM5 ! Series '3 Pr'0er#/ Wables, 'l. +), 1s# ed., Wa/l'r V Francis, Ue"is0here, >ashin(#'n, -.B, 19G7. H10I . . S/che), !.!. asser"an, .!. a('ruchen2', !.-. N'=l'), &.!. S0irid'n'), .!. Ws/"arn/, $er"'d/na"ic Pr'0er#ies '3 .e#hane (%a#i'nal S#andard Me3erence -a#a Ser)ice '3 #he 7SSM. ! series '3 0r'0er#/ #ables. 'l. 3), 1s# ed., S0rin(er, >ashin(#'n, -B, 19G7. H11I . . S/che), $er"'d/na"ic 0r'0er#ies '3 e#h/lene (%a#i'nal S#andard Me3erence -a#a Ser)ice '3 #he 7SSM5 ! Series '3 Pr'0er#/ Wables. 'l. 7), 1s# ed., Ue"is0here Publ. B'., >ashin(#'n, -B, 19G7. H1+I . . S/che), $er"'d/na"ic 0r'0er#ies '3 e#hane (%a#i'nal S#andard Me3erence -a#a Ser)ice '3 #he 7SSM5 ! Series '3 Pr'0er#/ Wables. 'l. C), 1s# ed., Ue"is0here Publ. B'., >ashin(#'n, -B, 19G7. H13I.. &ehri(, U. den#=, 0, , W 3'r ben=ene in #he ran(e 5 #' 300 .Pa and 3+3 #' 6G3 N, . Bhe". $er"'d/n. 9 (1977) CC5ZC50. H1CI&... >ils'n, *n#er0re#a#i'ns '3 Wr'u#'ns da1 in Mela#i'n #' Equa#i'n '3 S#a#e Pr'0er#ies, in5 N.B. Bha', M.d. M'bins'n (Eds.), Equa#i'ns '3 S#a#e, 1s# ed., !"erican Bhe"ical S'cie#/, >ashin(#'n, -B, 19G65 00. 5+0Z536. H15I&. Sch"id#, U. >en=el, ! "'di?ed )an der >aals #/0e equa#i'n '3 s#a#e, Bhe". En(. Sci. 35 (19G0) 1503Z151+. H16I!. Uar"ens, U. Nna00, $ree-0ara"e#er cubic equa#i'n '3 s#a#e 3'r n'r"al subs#ances, *nd. En(. Bhe". Funda". 19 (19G0) +91Z+9C. H17I%.B. Pa#el, !.S. We8a, ! %e1 Bubic Equa#i'n '3 S#a#e 3'r Fluids ans Fluid .i4#ures., Bhe". En(. Sci. 37 (19G+) C63ZC73. H1GI. .c&arr/, B'rrela#i'n and 0redic#i'n '3 #he )a0'r 0ressures '3 0ure liquids ')er lar(e 0ressure ran(es, *nd. En(. Bhe". Pr'cess -es. -e). ++ (19G3) 313Z3++. H19IM.B. Meid, ... Prausni#=, B.E. P'lin(, $e 0r'0er#ies '3 (ases and liquids, C#h ed., .c&ra1 Uill, %e1 <'r2, 19G7. H+0IB.F. S0encer, S.B. !dler, ! cri#ical re)ie1 '3 equa#i'ns 3'r 0redic#in( sa#ura#ed liquid densi#/, . Bhe". En(. -a#a. +3 (197G) G+ZG9. H+1IN. W'chi(i, Predic#i'n '3 hi(h-0ressure )a0'r-liquid equilibria b/ cubic equa#i'n '3 s#a#e, in5 !nnu. .ee#. S'c. Bhe". En(., %a('/a, 19GC. H++I!. e#ere, .e#h'ds 3'r #he es#i"a#i'n '3 cri#ical )'lu"es, Bhe". En(. . 35 (19G7) +15Z+17.

( + ! ) ( + ! )+ C ( ! ) (!.15) + (assu"in( #ha# g ` i, #he Z si(n a00lies 3'r , #he Y si(n 3'r ! ). $e s'lu#i'n 0r'cedure s#ar#s 3r'" assi(ned ('r #en#a#i)e) )alues '3 c , e,Z a5 calcula#e B (Eq. !.6) calcula#e , n, o, (Eqs. !.9 #' !.11) calcula#e ( Y ! ), ( ! ) (Eqs. !.13 and !.1C) calcula#e , ! (Eq. !.15) calcula#e ga, i (Eqs. !.7, !.G) calcula#e A (Eq. !.1+) calcula#e fa (Eq. !.5) *3 a 3ur#her c'ns#rain# is i"0'sed,i# is sa#is?ed b/ a s0eci?c )alue '3 Z a, 1hich is 3'und b/ #rial, and err'r. de# us c'nsider #he 0ar#icular case 1hen #he )alue '3 u Y w is assi(ned. $is (i)es rise #' #he equa#i'n5 +! + 1 + ! 1 B B (!.16) = u+w 1 + ! 1 "!=

*n #his case #he )alues '3 and ! need n'# be de#er"ined 'n each i#era#i'n. $e ab')e 0r'cedure is s#ar#ed n'1 1i#h a #en#a#i)e )alue '3 Z a and s#'00ed aXer #he ?rs# 3 s#e0s9 a chec2 is "ade acc'rdin( #' Eq.165 i3 n'# sa#is?ed, a ne1 )alue '3 Z a is assu"ed and #he 0r'cedure s#ar#ed a(ain. ;nl/ 1hen Eq. !.16 is sa#is?ed, #he 3ur#her s#e0s are e4ecu#ed. References H1I %.B. ar(aXi2, Wables 'n #he #henn'0h/sical 0r'0er#ies '3 liquid and (ases, Ue"is0here Publ. B'., >ashin(#'n, -B, 1975. H+I d.B. de1is, >.. Frederic2s, 'lu"e#ric 0r'0er#ies '3 su0ercri#ical h/dr'(en sul?de, . Bhe". En(. -a#a. 13 (196G) CG+ZCG5. H3I B.B. Usu, .. .cNe:a, Pressure - 'lu"e - We"0era#ure Pr'0er#ies '3 .e#h/l Bhl'ride., . Bhe". En(. -a#a. 9 (196C) C5Z51. HCI . . S/che), $er"'d/na"ic 0r'0er#ies '3 3re'ns (%a#i'nal S#andard Me3erence -a#a Ser)ice '3 #he 7SSM5 a Series '3 Pr'0er#/ Wables), 1s# ed., Ue"is0here Publ. B'., >ashin(#'n, -B, 19G7. H5I d. Uaar, .S. &alla(her, $er"'d/na"ic 0r'0er#ies '3 a""'nia, . Ph/s. Bhe". Me3. -a#a. 7 (197G) 635. H6I M... Neller, d.*. S#iel, $e P- -W beha)i'r '3 ace#'ne in #he dense (ase'us re(i'n, . Bhe". En(. -a#a. ++ (1977) +C1Z+C3. H7I M.S. Fin2els#ain, d.*. S#iel, $e P W beha)i'ur '3 "e#h-