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INSTITUT FRANC;AIS DU PETROLE PUBLICATIONS

JEAN VIDAL

THERMODYNAMICS
APPLICATIONS IN CHEMICAL ENGINEERING
AND THE PETROLEUM INDUSTRY

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Table of Contents

Preface V
Symbols XIX

1
Prindples. Thermodynamic FunctiOlu. The Ideal Gas

1.1 ncDnjtiOA5 , , .. "". I


I 2 The Fiat I..... 3
1.2.1 l1le Energy of. System " , ,....................................................... J
1.2.2 Energy Exchanges during a Transformation 4
1.2.3 Statement of the First Law Applied to a Ck>s<:d System.................................. 5
I Z 1 I General 5
J 11 2 t..... boriclhn.formotions 5
1.2.3.3 Ad·.bIIlie Compression "..... 5
I 2] 4 naNforma';""" 0' Cons"D' Pus"',... 6
U Applialion of the first Law 10 an O~n S)'5telD.............................................. 6
J1 I General 6
1.3.2 Sleady-State System, 8
I 4 De Second I.l!W 8
1.4.1 Enlropy........................................................................................................... 9
1.4.2 Relationship between Inlernal Energy and Enlropy 10
1.4.3 Application of !he Equilibrilll'l\ Condition 11
1.4.4 Slalisti"",1 Signifl(:ance of Enlropy 12
1.5 Helmholtz Energy .nd Gibbs Energy 12
1.6 TIlermoclynamk FUndion: InlenW Energy, EnthaJpy, Entropy,
HellDhollz Energy .nd Gibbs Enern 19
1.6.1 Dependence on Temperature, Volume, or PTes5ure 19
I 62 Cbaraetctistie Fllnctions 22
1.7 De Ideal Gas 23
1.7.1 Equation of Slate and 111ennodynamie Properties.......................................... 23
1.7.2 Heal Capacity................................................................................................. 25
1 71 Da!a ThblM 26
References 26
x TJbf<> 01 ConletllS

Properties or •Pure Substances

2.1 The Rellilionship bel"'"een Pre5SWl', Volume and TemperahlR'.


L1quid-V.por Equilibrium................................................................................... 29
2.2 Vapor Pressure...................................................................................................... 34
2.2.1 Liquid and Vapor 5Ial".................................................................................. 34
2.2.2 Vapor Pressure Eql,lalions ,................................... 36
2.2.2.1 Clapeyron Equa'ion................................................................................. 36
2.22.2 Empirical Com:la.ionI............................................................................. 37
2.3 Enlhalpy Diagram lind Hut or Vaporization 44
2.3.1 Dependence of Enthalpy on Pressure and Temperature.................................. 44
2.3.2 Heat of Vaporization 46
2.4 Cillculliition of1'bltrmody..mic Properti('5 "...................... 49
2.4.1 Residual Enthalpy........................................................................................... 50
2.4.2 Residual Gibbs Energy 51
2.43 Fugacity 53
2.4.4 Calculation orThennodynamic Properties in the Uquid Plla.se 54
2.4.5 General Equations 58
Condllsion 59
BltleRn,," 59

J
Predicting Thermodynamic Properties of Pure Substances.
General Prindples. CorrespondJng States.
Group Contributions

3.1 Techniques of Molerol.r Simul.lion.................................................................. 63


3.2 The Co"""spondinll States Prilldple................................................................... 64
3.2.1 Correlations Using the Critical Compressibility Factor 69
3' I I WilSOn Method 69
3.2.1.2 Rac~ell Equat;on 70
3.2.2 Condations Using the Acentr;c Factor 71
3" 1 Prediction of the Second Yinal Coeffant n
3.2.2.2 l'ropcl1ics.t Uquid·Vapor Equilibriurn...................................................... 74
3 2 2 1 l.A:e "M Keiilcr "'etbad "","''''. ""''''''". """"''''. "".."'''''''. """"'. .. .". 15
3.2.3 Extensions to the Corresponding States Principle "......................................... 81
3.2.3.1 Extension 10 PoI.r Compoundo "" " .."" " "" "" "... 81
3 2 1 2 Ellension 10 ""Ilures B2
3.2.4 Conclusion Conc<:rning the Corresponding States Principle............................ 83
rmle 01 Commrs XI

J.3 Slrudure Property COrttladODli 84


3.3.1 PropeRies of the Ideal Gas 85
332 Crilical Coo«lioates 88
3.3.3 Calculation of Molar Volume in the Liquid Pltase........................................... 90
3A ElUlIDples 01 Ihe Rellalionships Bel"'eell Tbl,'rmodYllamk Properties........... 90
3.4.1 Calculation of Critical Properties from Vapor Pressure and Density Data 90
3.4.2 Calculatiorl of the Heat OfVaponzalion:Wal$On Equalion 92
3.4.3 Empirical Equations Developed from the Normal Boiling Point and Densitv. 93
Copdusion 94
Relen:pca 95


Equlllions of Sllite

4.1 Equations 01 Stale Derived lrom the Virial De..elopmenl.............................. 102


4.L.I Volume Virial Equalion of Slale Truncated after the Second 1erm 105
4.1.2 Volume Virial Equalion of Slale Truncated after the ThirdTerm 106
4.L.3 Pressure ViTial Equalion of Slale Truncated after the Serond Thrm 106
4.1.4 11te Benedid. Webh,and Rubin Equalion....................................................... III
4.1 Equalions of Sllile Derived from tbe Van Del Waals 1beory 112
4.2.1 11te Soave-RedLich-Kwong and Peng·Robinson Equations 0(5tate................ 113
4.2.2 Recent Developments of Cubic Equations of State......................................... 124
".2.2.1 Depon<k"'" of Anraction Parameter '.' on Temperalure 125
4222 Mpdjfog"inns of lhe AllToc1joo Term 126
".;!.2.J Application of the Con<epl of Group Contribution 130
4.2.2.4 Eq .... tions ofSlOle for Rigid Spheres and Hard Chains.................................. 134
4.3 Sredne [qualtons of State for Certain Pure Substances 136
4.4 TbeTail Equalion................................................................................................. 138
RderrnCf:S 119

CbMraderizatjOD
• or Mixtures

5.1 Partial Molar VllIues in the Homogeneous Phase 144


5.1.1 Definitions. Main &lualions............................................................................ 144
5 I 2 Dctconinalioo or Parlial Molar Val"es 145
5.2 Chemical Potential 149
S2 I Definilion J 49
5.2.2 Equilibrium Condilioo Between P!tase........................................................... ISO
XII

5.2.3 Relationships between the Chemical Potential and the Olher'Thermooynamic


PTopeMlCS , 151
S.D.l The Gibbi·DulKm Equa'ion..................................................................... 151
S.2.3,2 Dcll"n<knce of Chemical !\>lcnlial on Pressu.c and Tempc lure IS I
S.2..3..3 ~,~~:::i,= belwecn 1M Chemical Potenl...l and the OIhe.Thenn~.mic:. 152

5.J Fupdty . 152


5 3 I Defin;t;on 152
5.3.2 Dependence of Fugacity on Temperature, Pra;sure. and Composition .. 153
5.4 Midng Vlllues Activily . 154
S 4 J Definitions " ,, ......""' ",, .. 154
5.4.2 Dependence of Activity On 1emperalure. Pussure.and Composition . 155
5.5 De Ideal Solution ......'"""....."....",,,,,,,.......,,, """,,,,,,,,,,,,,,,,..,,,,,.,,,,,"'''',,,,...,,,,, 156
5.6 Cakulalion of Jo'upcity , ,.."",.,..,..,,,.,,..,.".,,, ,.,, . 157
5.7 Er.:cess Values and Activity Coemdeou " " 159
5 7 I Definirions " .......... " " ........ ........ 159
5.72 Dependence of EKceu Values on Temperalure, Pressure, and Composilion .... 160
5.7,) Activily Coefrlcicnl$ " , ".,.." "".,,,,,,,,,.".,..,,,,,,,,,..,..,, 160
5.7.4 Dependence of AClivily Coefficicn15 on Temperature. Pressure. and
ComPOSItIon , " , ,.,,,,,.,,,,,,.,,,,,,,.,..,,,, ,, 161
5.8 Comparison ofTwo Meth0d5 fOl" Caku!aling Fugacity " . 163
5.9 Asymmetric Convention: the lIenry Coos••nl."".""""."."""""".."".." .."...... 165
Rrl'ef£Oce .. ..". ... .. ...
" "" ......... " " " " " , , , .. ,,,,,,,,,,, .. ,,,,,. ...",,,,,,, ........
", 166

Mixtures: Liquid- Vapor Equilibria



6.1 Descriplion of the Vapomalion or Condensation Phenomena...................... 168
6,1,1 Isobaric Liquid·Vapor Equilibrium Diagram ."""."........................................ 168
6.1,2 I$olhennal . uid-Va r E uilibrium Dia ramS. Evolulion wilh Tern rature
ntlC& IDI an elrogra on ensa IOn ".".. """", 171
6.1,) Azeolropic Systems........" ....""..""".".....".",................................................. 176
6.2 11Ie Uquid.Vapor EquiUbrillDl Conditioo. De Equilibrium Coemdent ..... 179
6.J Dependence of the Equilibrium Conditions on TempertltulY, Pressure,
llDd Composition ".".,,,,,,,,,.,,.",..,.,...................................... 184
6.3,1 Dependence or Bubble Pressure on Composition .""...................................... 184
6.3.2 De ndence or Bubble Pre~urc on Tern rature. Oa n ualion
PP Ie to a Ixturc """ " " .."." 186
6 3 3 Coherence Tnl " "",,,,,,,,,,,,.. ,,,,, .. ,,,,, ,,,, , ""."."""..... 187
6.3.4 Slability and Critical fuillt Conditions " "."""".""..""" """ 188
T~b/eofConten" XIII

6.4 UquHI·Vapor Eqwlibriom Probh~ms 190


6.4.1 At Given Tempcrntl.ln: (or Pressl.lre) and Vapomed Frnetion 192
6.4.2 At Given Ttmpcratl.lre and Preuure 192
6.4.3 ClUe Where One oftbe Data i$ a Thennodynamic Properly........................... 192
6.5 Calculation AlloridullS 192
6 S I Calculation of lhe Bubble Poim 193
6511 c.tm1"iOllo(lheB"bbIcPrc""", 193
65. L2 D.kulalion of lhe Bubble Ttmperaluu 194
652 CalculationoflbeDcwPoint " ' " 194
6 'i 2 I C1kulaljoo O(lbe Ikw Pre,«uu 195
65.2.2 D.lculalion 01 lhe o.. Ttmperature 195
6.S.3 Partial Vaporiution 195
6.5.4 Application to Ideal 5oIulion5......................................................................... 196
6 S S Nan·Id".l Snhnions 201
6'iSI Non.ltltIISolmionsalt".. Pre"u.,. 201
6'iS2 GrDcnlCa... 201
6.5.6 General Calculation Metbod of liquid Vapor Equilibria 203
6.6 Solubility of Gases in Liquids.............................................................................. 204
Referrpces 206

1
Deviations from Ideality in lhe Liquid Phase

L 1 E:tees..5 Ouanfll"" "." "." "."." "" "..""" """".."" " .."".." ..". 2! 0
7.1.1 E"cess Volume. E"cc$s Heal Capacity "................... 2! 0
1.1.2 Heal of Mi.ing " "............................................. 212
7.1.3 Excess Gibbs Energy and Activity Coefficients............................................... 214
1.2 Co~lation 01 Uquid Vapor Equilibria at Low PreSliure. Coherence Test... 218
7.3 InOuenct of VaTlI1 Molar Volume: tbe Combinatorial Term 223
7A The Concept of Local Composition "" " "" "."."" ""...... 227
14 I The l.all;Cl' Marlcl nq
7,4.2 The Quasi Chemical Modcl ".."", ,..""""""'"", "''''..,,.... 229
143 General Remarks 230
7.5 Regular Solutions.................................................................................................. 231
7.6 Empiritlll Models Based on the Concept of Load Cornpo5ition.................... 238
7.6.1 The Wilson Equal;on....................................................................................... 238
7.6.2 The NRTL Equalion 239
76 J The IINlal lAC Model 244
7.6.4 The Wilson. NRTL UNIQUAC Model.. Conclusion 246
XIV

7.7 Group Conlribulion M~lhods............................................................................. 248


77 I The ASOG Method 250
712 The IJNIFACMelbod 251
1.7.3 Group Contribution Method. Conclusion 257

7.8 ~lIted SoluliollS 258


7,9 IODic SolutiOnS .. "'""''' ",""" ..... " " , , , , ........ ..
,, 263
RefeD'Pces 265


Application of Equations of State '0 Mixtures.
Calculation of Uquid-Vapor Equilibria Under Pressure

ILl EJ.tensioD.~ o( the Correspondinx Slates Principle 270


8,1.1 Calculation Rules for Pseudocritical Points..................................................... 271
8.1.2 Calculation of Thermodynamic Properties and Fugacity Coefficient! in a
Mi~ture .., ,........................................................................................ 275

8.1 Varial EqWltion! or Stille lhlllCllted after tbe Second Term............................ 277
IU EqWllionli or Slate Derived rrom Ihe VIID der WIlIIJs Theory........................... 279
8.3.1 The Classical Mixing Rules............................................................................. 279
8.3.2 Calculation of Chemical Potentials and Fugacity Coefficients.,....................... 282
8.3.3 Application Range and Rnult! ........,.............................................................. 283
8.3.4 The Binary Imuaetion Parameter................................................................... 286
11.3.5 Allernative! on the Oauital Mixing Rule! 290
83.5.1 Dependence of the Allraclion Parameler 00 Composition............................. 290
83.5.2 Application of a Quadratic Milling Rule to.he Co,-olume ..,.......................... 291
8.3.6 Calculation of the Thennodynamic Properties of lhe Mixture......................... 292

8.4 Mixing Rules and [.<<!is Functions 292


8.4.1 Calculation of ExecS! \Iantitics Usin u.Btions of Stale:The Problem

8.4.2 Mixing Rules Derived from Excess Gibbs Energy at Infinite Presliure............ 298
8,4.3 Mixing Rules and Exuu Functions at Constant Packing Fraction 302
IU3.1 Formulation of uation. of Siale Derived from the "an derWaals
,n erms llC 111$ ractlOll 302
11.4.3.2 CakulalKm oflhe Helmholtz EOCTgy A...................................................... 303
8,.3.) Applkat;oo to a Mixlu,e and it! Componenls 304
8.•. 3.<1 Reoulto:Abdoul Group Contribution. Method............................................. 307
8.4.4 The MMHV2" Method 309
8.4.5 The Wong and Sandler Method....................................................................... 313
11.4.6 Advanta~cs and Disadvanta~n of Mixin~ LaW!! D<:rived from Models and
rilble 01 Con_IS XV

8.5 c.kaJallol:l of Liquid- Vapor Equilibria ] 16


8 ~ I Newton Method 319
8.5.2 Tangenl Plane Method.................................................................................... 321
COI:Idudol:l 324
Relerute!l 324

9
Liquid-Liquid and Liquid-Liquid-Vapor Equilibria

!U LiqWd-Uqwd Equilibria aad Del'lalloR!l from Ideality................................... 330


9.2 General Description of Uquld.Uqukt Equllibri.............................................. 331
9.2.1 Bin.ry S~Slems................................................................................................ 331
9.2.2 Ternary SySlems 334
9.] Seledlvily of the Uqwd·Uqwd Equilibrium ]37
9.4 Uquid.Uquid.V.por Equilibri........................................................................... 339
9.5 C.lntl.tjon Melbod, 345
9.6 Water, Hydrocllrbon Systenu; h.................. 348
9.6.1 TOlallmmiscibility Hypothesis: Cakulalion of the Three-P'h.asc Equilibrium.. 348
9.6.2 A lil'ation of E ualions of Slale to the Calculation of Phase uilibria for
aler y rocar ystems........................................................................... 351
Coodusion 352
Referrnte!l 352

III
fluid-Solid Equilibria. Crystallization. Hydnltes

10.1 Liquid-Solid Equilibrium Diagram 356


10.2 CakulallOI:l of Cry,lalliuliOI:l Equilibria 359
10.2.1 General Equations 359
10.2.2 Paraffin 9'ystalliution 363
10.23 Auid-.50lid Phase Transition al High Pressure 365
10,] Hydrates 367
10.3 1 Generalilies. 367
10.3.2 Phase: Diagrams.......................................................................................... 368
10.3.3 Cakulation of Hydrate Formation Equilibria 370
Relereptfl 3n
XVI

11
Polymer SolatioM and AUoys

11.1 Pmymcn in SoJulioD 377


11.1.1 TheAory-HugginsModel 317
11,12 The InOucnce of Free Volume .."". ,. " 379
11,1.3 'fbI' Entropic-FV Model............................................................................. 382
11,1.4 The GC·F1ory Model 383
11.15 The GCLF Equation of State (OrO\lp Contribution Lattice Auid) 386
11.1.6 Extension 10 Liquid·Liquid Equilibria........................................................ 389
11.2 Polymer Mixtures 389
Conclusiog 392
RefereDces 392

11.
MuUicomponent Mis:lures

l2.1 P.-udocomponenls 396


12.1.1 Comple~ Mi~lure Analvsis 396
12.1.2 Lumping..................................................................................................... 398
12.1.3 Thennoo)'namie Propenics of Pseudooomponents..................................... 400
12.1.4 Representing the Heavy Fraclion of Nalural GaKs.................................... 402
l2.2 Conllnuow; Thermodynamics 4()4
12 2 I IX:finjljOD 404
12.2.2 Chemical Potcntial. Fu aeit Coefflcienl. and uililnium Condition

12.2.3 Applicalion Examples 406


12.2.3.1 Uquid.Vapor Equ'librium in an Ideal Solution....................................... 406
12.2.3.2 Excess Gibbs Eneru of a Polymer SolUlion in SemicontinUOlli
n.crmody... mial............................................................................... 408
el .. deC~n<a'ion(>h a,ura .a$.A ica,ionof he
Soavoe·w. • won uallon 'ale............................................... 409
CondnsloQ 411
Rdcrt'D('fi 411

Chemin' Reactions

H.I lbermodtemialDltM 414


13.1.1 Standard Enthalpy of Fonnation. Standard Gibbs Energy of Formation 4.4
13.1.2 Application of Group Contribution Methods 4'6
T~bk 01 ComenlJ XVII

13.1.3 "Coherenf' Enthalpy Data 419


13.1.4 Siandard Enthalpy and Gibbs Energy of ReaClion 419
13.1.4.1 !:.2:'::"~i!nnd Cakulalion from Standard Enl"al~and Gibbs Ene~ 419

13.1.4.2 ~~~~u~~7.~:.~~~.~.~~.~.:~.~.~.~.;.~.~~.~.~~......... 420

13.2 Hut of Rt'actiollllad Energy Balance 421


13.2.1 HealofReaClion 421
13.2.2 Energy Balance of a Reaclor Or a Reacling Seclion.................................... 424
13.3 Chemical Equilibria 425
13.3.1 The Equilibrium Condilion 425
13 3 2 The lAW of Ma5.!5 Aetion "". """",,,,,,,..,, "".."",,,, ,,,,,,,,, ,,,,,,,,,,,,..... 426
13.3.3 The Laws of Equilibrium Displacement 429
13.4 Cakullltion of Simultaneous ChemlCIII Equilibria 431
ReferrDces 433

AppelldiJi 1
Datahase 435

ugaClty Jctent...... 443

Appendix 3
Surface Volume and Inleraclion Parameters Applied in the UNIFAC Method.. 4n
Appendix 4
Properties of the Ethane (I) Propane (2) S)'litem at 45°C and at 2.5 MPa as a
Funclion of Composition 479

Appeadix 5
Detailed Analysis of a Straight·Run Gasoline Cut 483

Appendix 6
1 [nilS 487

INDEX 489
Symbols

a .....a Alpbabel I : <;Q<)f(linatioo


number
" : molar Helmholtz energy I, : mole fraction of component j
• : equation of Siale parameter Z : compressibility factor
", : aetivhy of component I (ebap.e. 5)
A ; Hdmholt>; "neT&)' Glftk. "lplul~
b : equation of Slale parameter r : aeti"';ty roeff"lcienl
B : s.erond virial ooefrtci"nt Ii : solubility parameter
" : translation parameter in an equation of I) : molar, packing fraction
state 6 : temperature
C : binary parameter in an uceM Gibbs 6, : surface fraclion of component I
energy model (Oapler 7) j,I : cllemkaJ potential
£ : total energ)' (Chapter I) " : ~toichiomCll;C c:oefficient
f ; fugacity ~ : exlent of reaction
g : molar Gibbs elkrgy p : molar density
G : Gibbs energy fJ : fugacity ooefficient
h ; molar enthalpy <P : volume fraction
~ : Planck's constant .... : acentric factor
II :enlluo.lpy
Ie ; inl(mellon parameter (Chapler 8) SubsoipiS
of. : Bollzmann con.tanl c : critk~1 (mt;caltcmperature. T<, elc.)
K : equilibrium corn;lanl cal : calculated
M : molar maSS exp : experimental
/I : nllmber of componcn15 / : formation (enthalpy of formation,M"I'
N : nllmber of moln elc.)
P : pressure !,j : component
po : vapor pressure k./ :group
" : Poyntingcorrection P : al oonSlant pressure
q/ :surface parameter of component i T : al oonSlant temperature
Q : ~al quantity V : al COMtant volume
Q. : surface parameter of group k
., : V<llume parameter of component i
R : ioka! gas constant
,
R. : volume parameter of group k
: molar entropy
•• : alliolllural;OO
: reference state
S : entropy • : ~tandard stille

u
T : absolute temperatur"
: molar internal energy
•;. : ideal gas stale
: ideal5OlutiOll
U : internal energy £ :excess property
v : molar volume L : liquid state
V : volume M : rnixillJl property
00', ; mass fraction V : ".por ~tate
W :work.
x, : mole fraction of component i in the Hquid Operat...,

y,
p'-
: mole £raetion of component i in tile vapor
exp ;exponential: up (x). C"
In : naturallozarithrn
pllaw 1"110: b;uc: 10 logarithm
I
1 Principles
Thermodynamic Functions
The Ideal Gas

It would be inaccurate to say thai the development of thennodynamics is not based on


experimentation. II is from observation thai the concepts of quantity of heal, of tempera-
lure, of energy of II system. and of irreversibility have been c1cveloped. However, there was
an importanlluming lXlinl when the statements orlhe first and second laws allowed us not
only to "condense" the observations that produced them, but also to establish a priori la....'5
that subsequent observations have verified, to generalize from them and diversify the field
of their application. The greatest diversity cKists, however. within the field of thermody-
namics. Mechanical engineers, energy specialists.. and chemists apply the Slime principles..
but they have constructed their own conventions renecting lheir practical concerns.
Many statemenlS of Ihese principles can be sel forth and il is nOllhe goal of lhis chapter
10 enumerate them or to demonslrale lheir equivalence. For lhe most part. they arc famil-
iar 10 the reader who may. if he 50 wishes. consult lhe general references listed in lhe bibli·
ography.ln this chapter. we will limit ourselves to a few lopics emphasizing the points lhal
seem most imporlanlto us for the rest of this study.
First. we must review the lerminology proper to lhermodynamics. We derive our inspi-
ration rrom the teachings of A. Pl!ncloux 119921.

1.1 DEFINITIONS

Thermodynamics applies to a physical entity. lhe "s}"Slem". possibly composed or distinct


parts. or "subsyslems-. The system is defined only if its physical limitalions or "bound.
aries- are specified. as well as the nalure of lhe exchanges lhat il may maintain with the
rest or lhe universe (..the surroullodinp"). The syslem is termed "dowd~ or "open" accord-
ing 10 whether or nOI exchanges of maller arc possible. For cltample. ils properties may
change duc to differences of tcmpeTlllure or pressure belween the syslem and lhe sur-
roundings. Its boundaries on the other hand may reSiSl such IranSfOrmalions. The energy
exchanges ,,'Ith the SUTroundinp will therefore havc 10 be specified according 10 the
exchanges or mailer. Similarly. certain changes may be excluded by virtue of internal
,
oonslrllints: first and foremost. those changes defining the possible bollndaries of sllbs~­
tems lhat may be rued or mobile. adiabatic or diathermic. impermeable or porous. It is also
well known thai ccrtllin chemical reactions occur onl)' wilh a calalrst or an iniliator. Ihal
olher reactions may be inhibited and. for example. 1hal we may apply Ihe laws of thermo-
dynamics to the solubility of air in hydrocarbons withollt being concerned 300m the possi-
bility of comhustion. As with boundaries. tllese constraints must also be specified in order
to describe 11 "system" and lhc changes that we may expect or exclude.

The most nalural subsystems thai we can define are made up of the phases into which
maHer is organi:red. In panicular. we slllll1 sllIdy Ihe equilibria between the liquid and
vapor phases. A "pbllse" forms a "homogeneous" physical entity in thc sense that all the
parts of equal volume have the &amc properties (they have the same quantity of malter,
the same composition, etc.).

With a defined system. in principlc wc may describe its "5111"" by dctermining its ~pro,.
crttes. or stille '"II.lucs", meaning the entirety of what is "observable": temperawre. pres-
sure, volumc, quantity of maller, and composition. for example. These properties are not
totally independent. and we Itnow very weHthat the volume occupied b)' a system is fixed
from the moment we Itno'" the quantities of each component, the pressure. and the tem-
perawre.

Within the scope of this te~t, these properties can be defined only for "slelld}·oSllIlc" sys·
terns whose slate does not change over the course of time (and whose state does nOt
depend on its development), In fact. this steady-state is often due to the e~istence of
appropriate boundaries or constraints. and insofar as these boundaries are precisely
described, we will state that the system is in a state of "equilibrium", This means that the
system will return to this state after any infinitesimal disturbance with respect to its bound·
aries-A state of equilibrium depends on the constraints imposed on the system:eonstraints
which we will talte into account when defining and applying the conditions of equilibrium
stated in the laws of thermodynamics.

Some of these properties are "additive" in the sense that if we nawrally or artificially
divide thc syslCm into several parts. such a property of the whole is calculated by using the
sum of the values of this property in each of the parts. For a homogeneous system. this
value is proportional to the size of the system, namely the quantity of matter. Volume is the
simplest cxample of such a property. but it is the same for internal energy. entropy. etc..
which we will define later. Such properties are termed ·'c.:tensi"c" and we shall consis-
tently denote them by the capital letter symbols V. U. S. cte.
On the other hllfld. other properties in a homogeneous 5ystcm arc independent of the
size of the s)·stem: density. pressure, temperatuTC. cte. They are termcd "iutensh'c" and on
this subject, we recall the definition given by Pc!ncloux [1992]: "phase fcfefli to the entirety
of intensive properties". Among these properties arc some that govern the equilibrium
among the various parts of a syStem. If twO parts arc separated by a mobile boundary. the
pressures must be the same in each part.ll is the &ame with temperatures if the boundary
is diathermic. and with the chemical potential (which we shall define in Chapter 5) of each
component if the boundary does not resist exchanges of matu::r. Such intensive properties
are "potentials" and intervene in conjunction with corresponding extensive properties:
volume, entropy, and quantities of mailer. There are other intensive properties defined by
3

lhe value taken by an extensive propcny for Ihe unit of mailer (one mole): molar volume.
molar heat capacity. etc. These are sometimes referred to as "densilies~. We shall give them
the same symbols. but in lower case: v, molar volume. II, internal molar energy. elc.

If ceflain constraints thai assure the equilibrium of a system aTc removed. lhe system
generally undergoes a "Innsformlilion", and changes via a series of intermediate states 10
a new state of equilibrium. This ,hangc I;l(1;lITS by variation of its properties. and. in gen·
eraL by "energy exdlllnKH" with lhe surroufldings. such as the work done by pressure. if ilS
volume changes. for example. In some cases. we can imagine thallhe opposite progression
might be possible. II would then be a "",vII'Qible" transformation. and in panicular. il
might occur via a series of closely related states of equilibrium in wlliclltlle properties of
tile system do not cllange from one state to tile next except in a finite manner. We arc lllen
speaking about a '"quasistalic:" transformation. To accomplislltllis.tlle motive agenlS of tllis
transformation will c:ontinually adapt to tile state of tile system. Sucll is tile case witll a
compression process during wllicll tile extemal pressure remains practically equal 10 tllat
of tile system, or witll a transfonnation due to an infinitesimal differenlX in temperature.

1.2 THE FIRST LAW

1.2.1 The Energy of a System

The first law is based on attributing an extensive property to any closed material system,
namety energy. and on the establishmenl of an exaet balance between the variations of this
properly during tile course of a transformation on tile one Iland. and on the other. tile
work accumplislled by the surrounding environment due to mechanical. electrical. and
magnetic forces. as well as so-called heat exchanges caused by differences in temperature.

Certain components of energy are familiar and independent of tile internal structure of
the system. In the first place. they involve p<ltenlillJ energy in the gravitational field £1"""
which is expressed as a function of mass m. the acceleration of gravity g. and the calculaled
elevation compared to an arbitrary reference Z. It is the same for the kineli<: t'neTV of the
entire system. £~m' that is related to ma5S.,to tht' moment of inertia, and to the speed of the
system.

Mechanics is a function of these components. In themlodynamics we also take into


aceount""intemal energy"", U, which originates from:
• First and foremost, the kinetic energy tllatll.ccompanies the random movement of the
molecules that make up the syslem (translalion, rotation of all or pari of lhe mole-
cule, longitudinal or transversal vibrations of the interatomic bonds), Ii determines
the properties of lhe '"ideal gas"".
• Secondly. the intennolecular cohesive energy related to the forces of altraclion lind
repulsion between the molecules. Opposing the disordered kinetic agitation of mole-
cules. they contribute 10 the organization of maHer in different phases.
• And finally. the interatomic cohesive energy thaI assures the stability of the molecu·
lar structure and is evidenl during chemical reactions.

p'
4

• Of course. it would be appropriate to quantify the intra·atomic cohesive energies that


are much mOTC numerous. but they do not occur in the phenomena studied here thai
preserve the structure of the Dtom.
As with the potential energy in the gravitational field. internal energy can be calculated
only in relation to an arbitrary reference.
We therefore write:
£ '" Epc>< + E~j" + U (1.1)

In the problems we present here. m05t oftell the variations of potential energy in the
gravitational field and in the kinetic energy of the system will be leTO or negligible. The
variations of system energy will be reduced to variations of internal energy.

1.2.2 Energy Exchanges during a Transformation

When the system in question changes from one Slale of equilibrium to a new stale of equi-
librium due to the removal of certain constraints that insured the stability of the initial
state. this transformation is accompanied b), energ), exchanges with the surrounding envi-
ronment. We shall now attempt to specif)' the nature of these exchanges- For the most part,
the)' are altributable to external forces acting on the system. and in particular, to Ihe forces
of pressure.lrthe pressure acting on the s)'stem is designated p...,. the work supplied to the
system Clln be expressed by the equation:

DlV =-1~" dV (1.2)

For this tmnsformatioll to be reversible. it is necessary that the pressure acting on the
system p•., be equal to the prevailing pressure within the system P. and the work dW_
will then be cqual to:
SW... =-PdV (1.3)

If we take into account the sign of the variation of volume dV that is related to the vIII-
ues of p... and P respectivel)'. we can easil)' convince ourselves that:

DlV ... 8IV... or OW"'-PdV (1.4)

It is similarl), appropriate to point out. for example. the work due to the presence of
electrical and magnetic fields surrounding the S)'l'lem.ln general the)' will be absent from
the transformations that we will stud)', and as a reminder we shall designate them here as
W'.
We also know Ihat. due to the difference in temperature between the surrounding envi-
ronment and the S)'l'tem.the state of the system rna)' change. It is customary to state that
the surrounding environment "provides heat" to the system. Certainly this statement is
incorrect as neither the surroundings nor the system possesses heat. Nevertheless. we
retain this term as it has passed into practice and is unambiguous. These heat exchanges
Shall be designated h)' Q. or for an infinitesimal transformation. b)' OQ.
1. f'r;"dples. ThonKJdynamic Func:,iorn. """ kiNl Gas 5

1.2.3 Statement of the First Law Applied to a Closed System

1.2.3.1 General
TIle ftrJI ....., applied 10. dosed syslem,est.bUsMs ... eltJld balance boetWft.. lbe \'aliItio"
01 the 10taJ eDe1JY 01 the system dari"a'''Y tramlormation. ~niWe 01" lrn"ersible. and
lhe total_rk. and lbe qlllDtit~ Glhe.t Ib$orbed by thl! system:
<1E_I1(E,..+Eklo +U)_W+W'+Q (1.5)

lite symbol 11 daip.les e"Mrgy nn.Uon: E_ - E_,


Very often. when retaining only the internal energy ...ariation!!.. tbe work done by pres-
sure and the thennal uehanges. wc shall write the equation in the fonn:
(1.6a)

or. for an infinitesimal change. as:


dU",(jQ+5W' (1.6b)

At this point. it is appropriate to consider a few particular cases that colTcspond to this
simplified ...ersion of the firsllaw.

1.2,3,2 lsochoric Transformations

If the transfonnation in question takes place at constant YOlume and the work done by
pressure is equal to zero. the preceding equation is redlll;:ed to:
/J,Uv"'Q .. (l.7a)

or. ror an infinitesimal change. 10:


(l.7b)

The thennal e:o;changes accompanying an isochoric transfonnation therefore corre-


spond to the ...ariat;on of the internal energy of the system.
If this transfonnation has as its only dfe<:t a ...ariation in the temperalure of the system
(Ihere is neither a change in phase nor a chemicallransfonnation). the heat exchanges may
thcn be e:o;prcssed as a [unction of the heal capacity al conslant YOlume. CO', and of Ihe
temperature ...ariation:
( 1.8)

1.2.3.3 Adiabatic Compression


In Ihis case. thermal exchanges equal zero. and the work done by adiabalic compTC5Sion is
upressed as:
(1.9)

1.2.3.4 Transformations at Constant Pressure
Ir the eKlernal pressure is constant. and the system is in pressure equilibrium with the sur-
roundings at bmh the onset and allhe end of this lransfonnalion.lhe work done by pre$-
sure is expressed by lhe equation;
lY,.=_P«. L\V (1.10)
and. if we tate into account the pressure equilibrium conditions at both the beginning and
allhe cnd of Ihe transformation. we can write:
POl' lI.V=L\(PV),.
where P stands for the s)"llcm pressure. such lhal Ihe first law 3110....11 us to caleulate the
quantity of heal exchanged:
(1.11)
TIle sum U.;. PV is the "enlhldpy" of the system. [\ is an extensive property just like
internal energy and volume. It is more commonly used in practical calculations because
the prcvioWi equation relales thc!;!: variations to isobaric hcal Cllehanges. II is also used in
thc cllpression of the first law applied to open systcms. as we shall see subsequenlly.ll is
designated by the symbol H:
H=U+PV (1.12)
such that we can write:
(1.13)
Thcreforc thc quantities of heat nccessary for fusion. for lhe vaporization of a pure sub-
stance. or for a chemical reaction performcd at constant pressure will oflen be called
"enthalpy of fusion" (negative of lhe enlhalpy of melting), "cnthalpy of vaporization" or
··enthalpy of reaction". If lhc only cffcct of the transformation is 10 ellUse a varialion in
systcm temperature, it would seem lhat the elementary enthalpy variation is expressed as
a function of heat capacity at constant pressure. and may then be written as:
(1.14)

1.3 APPLICATION Of THE fiRST LAW TO AN OPEN SYSTEM

1.3.1 General

We have made il clear lhat lhc preceding equations relme to a closed system that does not
ellchange matter with the surroundings. In practice. however. such exchanges are the rule
and it is appropriate to accounl for lhe energy conlained within the flows of matter that
enter into or exit from lhe syslem in question, just as we will have 10 include their mass in
establishing a balance of mass.
Examples of open systems are varieu: a b"lIoon that .....e blow up. a reservoir that we fiJI,
a section of a pipeline. or a turbine. Seyeral of these examples can be combined to make up
a less elementary open syslem. A distillation column, a chemical rcactor. or a moving car
7

are other cases. In such systems. neilher the pressure nor the temperature arc uniform:
they change in splice and time.
During a shorl interval of time, ell. the kinctic energy, the pQtential energy in the gravi-
tational field. the internal energy of the system. and the mass of the sysu:m will vary. They
vary according to the type of content. mechanical work. and Ihe heal and modifications of
the system properties (pressure. temperature. nature of components).
The system can be defined initially by the position of its boundaries (certain of which
are real. other.; imaginary). For example. a unit of pipeline will be marked between two
dearly indicated sections. We will denote flows of maIler dm j • where III is mass. and assign
them a positive value if mailer enters into tile system. and a negative one if flows are lea...•
ing the system. We can also account for in~tantaneous outflows; dm;" D/ck Each flow i~
characterized by a certain number of properties: potential energy E"",J' kinetic energy
Ek .... , temperature T;, pressure P,. and, gi...en here per unit of mass: ...olume v;. internal
energy II;. and enthalpy II;.
Heat transfers emanating from sources with temperature T, will. however. be denoted
by l'JQj'
Other energy transfers., OW. will also be excluded. for ellOample, the work done by pres·
sure accompanying the possible variation in ...olume of the system (a balloon being blown
up). the energy supplied by the motor of a pump, etc. Howe...er. at this le ...el we shall not
exclude the work aCl:ompanying tile transfer of mailer.
The lOtal energy of the system £0 is:
~"'~."",+~.k~+~ (1.1)
Transfer of maller is broken down into two steps. Mass dm; occupies a ...olume II/ dm/.
and possesses an internal energy ,,;dm/.
First. we shall unite the system ilSelf with the mass dm" This step therefore increases the
mass of the system by dm/. and its energy by:
dEo '" 1'1"".1 dm, + ckin,i dm; + u/ dm l

This step is not accompanied by work done by pressure: the ...olume of the system has.
howe...er, ...aried by + "I dm/"
In the second step. we will reduce the new system formed in this way to its initial bound-
aries. The variation in ...olume will therdore be -IIi dill; and the work that we must supply
P/II/ dmi' The tran~fer of maller therefore is accompanied by a total amount of energy
equi...alent 10:
e 1"".'·dm·+e,·
, ".'
'''''''+'''''''',+
"
P,"."'".=(h.+c
""
.+c,.....,)dm,
pol.'

In the total balancc that describes the energy ...ariation of the system, we will sum these
elementary transfers., as ....ell as those corresponding to the work performed on the system
and the quantities of heat:
dEo = L (h/+cpol./+Clio,/)dt,,/+ L 6Q;+ L OW. (1.IS)
, J'
This ...ery general expression of tile first law ob...iously must be adapted to each particu-
lar case.
8 I. Principles. ~mk FunaioM. n,., 1d&J/ Cd>-

1.3.2 Steady·State Systems

We say lhal an open system is in a steady-stale when there is no variation on any point in
the quantity of mailer or energy. over lime. Temperature, pre$Sure. and composition may
vary from one point to the neXI within the system. but remain on all points invariable over
lime.
The previous equation therefore may be integrated oyer any time pcriod 61 wilh
dEo '" O. We denote by Q the quantity of total /leat supplied to the system during this time
span. by W the sum of work (other than that corresponding to Ihe transfer of matter), by
112 the enthalpy of the nows of mailer leaving the system, and by HI the enthalpy of llle
nOWl; of matter entering into the system:
H 1 =-L.Il;D1trJ if Dj '" 0 (dlll i '" 0)
If l " + L.h j D i 6J if 0; ~ 0 (d",." 0)

However. we will exclude the variations in kinetic and potential energy of these flows of
maLter. Undcr Lhcse conditions. the energy balance is wrillen as:
(1.16)

Applit'4 to /In 0lH'n Iystem in 5teadY1tllte. Illtd, inasmodJ ItS the "Ilrilltiom; of polenl..1
energy in tlte gnvitlltiOnal field Ilnd Ihe kinetic enere of lhe flow of mlltt" lIUIy be
esdudt'4.lhe Rnllaw eslablishes lID e:oct ba!aDee belween the """lI.tlon of entlullpy from
lite enlry Into. 10 Ihe e:Q1 from the Iplem Oft tlte one haneI. Ilnd on tlte olher band lite
q..... tltift of hut and the work absorbed by tbe 5}"l1fem elldudi"l Ihose IK:almpllnying
exdJllnga of mlltler.
This equation is closely related to the equation expressing the first law for a closed sys-
tem. Enthalpy has been substituted for internal energy (to include the work of transfer).
Moreover. the operator <l. here corresponds to the difference produced between ellit from
and entry into the system. while in a closed system. it CQrresponds to the difference
between the final state and ttle initial state. We must also recognize the importance of the
fundion of enthalpy. The energy balances of open systems in steady-state arc enthalpic
balances. In this way. for example. the variation in enthalp}' will correspond to the work of
adiabatic compression. or even to the heat balance of an item in the absence of work other
Lhan transfer work. finally, flow that takes place without eschange of heat or work is called
~isenthalpicR.

1.4 THE SECOND LAW

The first law in no way permits us to specify how the energy exchanges arc distributed
(work done by pressure. heat. etc.) during the course of a transformation. It expresses only
Ihe total energy exchange. However. we have seen Ihat the work done by pressure is at
least equal to an attained limit in eases of reversible change. Are heat transfers also lim-
ited?
9

We know that the 5lcadY-!ilale of a system is assured only by the cllistence of appropri-
ate boundaries. If some are removed, the system will evolve toward a new state and the
revcl"!iC change will nOi be possible. Given two Siales, it is therefore important [0 know
which one is favored. It is equally importantlo specify the conditions that the properties of
the system must satisfy in order for its state 10 be favored in relation to ailiransformations
respecting cerlain conditions (transformations at constant temperalUre or prc5Sure. for
example), and that it is in a SIMe of equilibrium.
II is to such qucSiions thaI the second law of thermodynamics responds. Its statement
varieli considerably from one author to another, and an 'n-depth analysis sho...."S that it is in
facl inseparable from the fil1il law.

1.4.1 Entropy

The statement of the seCQnd principle. the definition of the function of entropy lind that of
the absolute temperature scale. are inseparable:
Given a s)'!Ilem described by ih yolume. internal encorgy, and the " ....tity of maner for
eadl of ih oomponents. there emil a property of the 5)'!1lem.lI'ntropy S:
• II is an ulCO,w", fllllClion•
• During a lnlnsl'onn.tion Its ... rillion.~ a .... broken dOlm Inlo 11'1'0 lenns:
dS.clSj+dS~ (1.11)

The term cIS. is relaled 10 heal ellmange by thi!' "'IlUltion:

cIS.
6Q
, T (1.18)

wbll're T is a property of the syllem th.I dcopends 5Olll'ly on lis IlI'mpenotare, and "II' deslg·
natll' tbis property as "ab50lute lempenotu.......
IiSj is • tconn reblted to Inlernal moditicatioM of lhe Iyllem. II is " ... ays po5illve for
spontlncoltS tl'1lJ\ljfonnaliollS, ....d u:ro for reversible tl'1lrulfornutions.
clSj;oo 0 (1.19)
6Q
COfl!lCquenlly: dS.- (1.20)
T

The previous definitions leave the signs undetermined (which are related) for absolute
temperature and for entropy. As a convention. we state T> O.
We see later on that the properties of low density nuid allow us to determine the rela·
tionship of two absolutll' temperatures. The absolute scale willthercfore be filled by adopt-
Ing a filled point: by convention we state:
T= 213.16 at the triple point of water

II .~.rs that for lUI Isoblled system. and tberefore In lhe abllellCe of hut umanse
with the lunoundinp. entropy can InCTeISll' only duri... ine1lenible procases and stabi_
10 ,. Principles. rI>tYmodrfldlllic FmlClioits. the Ide<II G.>s

liz~
iliielf al II maximum l'lIl1te ,,-hen «juilibrium is 1I1tliined. or oourw. in the caR .fhut
ndunge. enlropy mllY dene~.
Moreover. the Equation (1.20) may be wnllcn as:
(1.21)

and thus corresponds 10 the limit mentioned earlier (Eq. 1.4) for the work done by pres-
SUfe:

SWia'-PdV (1.4)

1.4.2 Relationship between Internal Energy and Entropy

The variation or internal energy between two stalcs may be arrived al by observing any
transformation connecting the 11'0'0 states. We may do this using a ql,lOSiSt3tic transronna-
lion during which. if the work done to the system is limited 10 the work done by pre5Sure.
we will always have:
o'tV,=-PdV and lKl,= TdS (1.22)

We therefore obtain the fundamental expressions thai tie the first and second law
together:
dU",TdS-PdV (1.230)

I f>
and: dS= -dU+ -dV (1.24a)
T T
1111:$1: equalions generally perlain 10 one mole:

dll=Tds-Pd" (l.23b)

1 P
w .. -d"+-d,, (l.24b)
T T
Of COUI"SC. if Olhcr forms of energy transfer inlervene (for example. due 10 Ihe existence
of an elcclromotive force). il is appropriate 10 take them into accounl and we would wrile:

(1.25)

Wilhin lhC$I: expressions appear the intensive values. or polentials. p. 1: Fl' and lhe
eXlensive values with whieh they are associated S. V. and 1/.
These equations in no way allow for the calculation of work done 011 the system or the
heat transfen during the course of any process. We can stllte ollly:

(1.26)

p'
1. Principles. Jhermodyn.lmic F!Jf>CIiom. The ~I ~ II

1.4.3 Application of the Equilibrium Condition

This equilibrium condilion shall be ilIuslTated using an isolaled systcm, namely one that
e:llchanges neither heat nor work (of any kind) with the surroundings:
dW=O.dQ"'O

The inlcrnal energy and Ihe volume are therefore oonstanl:


dU",O.dV=O

and. according 10 the seoond law. entrop)' can only increase or be al ma:llimum:
dS~O

We will splillhis system into Iwo subsystems A and B, using a panition that will be fi:lled
initially. adiabatic, and impervious to all flow of mailer such thai each of Ihese two subsys-
tems is also isolated. On either side of the partition temperature, pressure. and composi-
tion may be differenl.
Let us now suppose that the panition is diathermic. that is to 58y that it allows for heat
flow. As internal energy and the entropy are e:lltensive functions and the system is isolated.
we have:

We shall express the entropy varialions of each pan A and B by applying Equa-
tion 1.24a. Since the volumes V A and V II are unchanged and the tOlal internal energy is
oonstanl, we obtaio:

AJ;,entropy can only increase. the result is thai dUA and T,4 - "f/j are opposite in sign. If
we now suppose that the partition is at the same lime diathermic and mobile, we must take
into account the variations in volume dV,4 and dV/j' which are related:

dVA + dVIl = 0

and would write:


dS" dS,4 + dS/j
and thus:

and, finally:

(T,4' Til')
dS. - - - dUA + - - - dV,. (P,TA T,Po)
The maximum condition imposed on tile system by the second law thus yields the
equality of temperatures and pressures.
J2 1. Principles. 11>cm>ody""mi<; function•. The Ideal ~

Finally. if we had considered thaI the partition separating the two subsystems WIIS not
impermeable. we would have had [0 use the derivatives of entropy as related 10 quantities
of maner.and would have established the condition of equality of chemical potentials. This
condition will be examined later (Chapter 5).

1.4.4 Statistical Significance of Entropy

In statistical thermodynamics I'"e can calculate the number of configurations 'Wlhat II sys-
tem cin assume, given the energy and volume. It is possible to show thaI this number is
related to entropy by the equation;
(1.27)
.( being the Boltzmann conslant.
In this way entropy is II measure of the disorder of the system. of its indetermination.
This equation must be retained in order 10 interpret the sign of the variations of entropy
.....ith vohime, the entropy of mixing (Chapter S). and to establish the expression of combi-
natorial entropy (Chapter 7).

1.5 HELMHOLTZ ENERGY AND GIBBS ENERGY

We have examined the condition of equilibrium and change in an isolated system. Any
possible change may be characterized as internal rearrangement. and is possible only with
an increase in entropy. In prnctice. we will deal with transformations during which the sys-
tem exchanges heat and work with the surroundings.. In order to take these exchanges into
aCCOllnt. we relate the t.....o equations:
dU=liQ+c5W+oW'
in which t5W' represents the work done by pressure and c5W' the other work (electrical,
etc.). and;
l5Q ~ TdS (1.21)
Substituting liQ we obtain:
OW+ oW' .. dU-TdS
l)uring the course of a change at constant temperature. this equation may be wrinen lIS;
O\v +.5\\1' .. d(U - TSh or w + W' .. tJJ.U - TSh (1.28)
Furthermore. if the system changes at constant volume. then the work of pressure force
is zero and this equation becomes:
bl¥'''d(U-TS)rv or W'''A(U-TS)
at constant temperature and volume
The function:
A=U-TS (1.29)
is called the Helmholtz energy.
13

l'he preceding equations are therefore wrilh:n as:


OW';;lo dAr,l' or W· ... llA
al constant lemperature and volume (1.30)

A cbaD,e at collS'anl lemper1ltu~ .nd l'olume is themore posslbIe oilly if the


Helmholn. ellC'''IY dKreale$. In Ihill caw, the s)"!Ilem may ~l'e off II quantity of encrz:y
l-W') to lite sunvundinl' lhal is at mOllI e,UII' to lhe d~_lll the Helmholn. eMrgy.1f
the Helmhohz energy inCftllSeS, ror the (:hante to be possible. It ...o.kI be nettSUry to
",pply 10 11M: .JY$lem (in the form of eledrial energy. for enmple) II qaantity of eMflY
lhal is III ie_I e(j .... 10 the illa't:ase in the Helmholtz enere- 5il1ft ~ are presumlnllhat
tbere are no such ndla:np hen', ...e sh.1l retain lbe cortdltlon of dumge:
dAT.V"O (1.31)

and the rolldilton of equilibrium:


( 1.32)

If the system changes al con$lllni tcmpenture ...... pn'SSure. and In pressure equilibrium
with the surroundings. the work done by pressure is then cltpressed by the equations:
OW=-PdV or

such Ihal we would write Equation 1.28 as:


SW'o-d(U+PV-TSh.p or W'o-d(U+PV-TS)
at constant temperature and pressure
The function:
G", U+ PV- TS", H- TS",A + PV (1.33)

is called the Gibbs energy.


The previous equations therefore may be wrinen as:
liW' 0- dG T.P or W' 0- tJ.G
at constanttcmpcralUrc and prcssurc (1.34)
ThWl, I mlnge lit oollStanl lempt'n1lure lind pre5!iure is pofiSible only if 1M Gibb!i
ene'1Y decnasa. In Ihis CMe. 1M I)'stem mllY «i"e orr. quantity of e_'IJ (-HI') to lite
surrollDdiap thIIl Is at IIIO$t equll 10 this decrelSof. If Ihe Gibbs eM'1Y lnCftucs, for the
duutge to be possible,it wouW be necnsary 10 supply 10 tlte ~em (ill the fonn of elKtri-
all enelJY. for eumple) a quanllty of tlle'1Y that is II ItItSI tq.... to tlte increase in lite
Gibbs tntrgy.
Since we presume that there are no such exchanges. we shall retain the condition of
change:
(1.35)

.nd tbe oondilion of equilibrium:


dGTJ'''' ° ( 1.36)

or more precisely. minimum G at constant temperature and pressure.


o EXAMPLE 1.1
Condensation by dclidbiJIic expansion
To illustmte the use of thermodynamic properties in the calculation of compression
work and heat exchanges. we will examine an ethylene condensation process that
functions according to the sleps lhat follow.
Ethylene. available at atmospheric pressure and at lorrF (37.8"C). is compressed in
an isothermal fashion to 50 bar. The fluid then undergoes adiabatic expansion to
return to atmospheric pressure. During this expansion. there is partial condensation:
the vapor phasc is recycled.
It is necessary to calculate the proportion of liquefied ethylene, the work and heat
ellchanges accomp.1nying the compression step. and the work that may be collected
during clI"pansion. To do this. we make lISC of a diagram (Fig. 1.1) that provides the
prcssure variation. shown on the ordinate. as a funclion of enthalpy. shown on the
abscissa. along the isothermal or isentropic curves. These calculations will force us to
makc certain hypothcses relative to the revcrsibility of each step. Most often. the laws
of thermodynamics do nOI allow us to estimate the exchanges of heat and work
except in the case of reversibility.

, <orr
',,7....,~ ' .•l.!.', ~~< ' . .' i' ...f /

. '~ ,~- . . '~', ',~"'


ti~-':t<:;<:,c,
""" ~ ~

000
000 -- - -~ - "
""
'" T- . .
- " ., ,~
'1:"" - I .' ;';'-ii: ,J' I, " ,'.1
- roo

J ., Le",
., i/ . J
I I
; I 7% (','/,\ ' ,J:.... ',
",.,/1' ',' \.

......
100
• ":-1 -
,- " ,~ ,
~

~
• 120-
-><.;j ... ' .~n ~ 1"'," , 9
, •
.- , ,.r., ,,,
'" f'-
__ 140 I
I I ,. I
, '.
'" ,,, ,, ,,'
,
'" ,. ,. I I , "
,, I

'"
J
...
I II ,.

"""
~~~I1':Y'
'''''' """
V ,

)lpre 1.1 Diagram of ethylene enthalpy pressure


[C.njar and Manning. 19611.
c,

uatl0n~

.-
(f
h'
Th,_ ~,

!l!i,"1IiC'CS'
OLI, '.•

, 'h,
,
I JU

~l au
16

and thence derive:


h""'-h 1020-990
(1.39)
m hV.tJ_h L " = 1020-815 =0.146
To determine energy exchanges during the isothermal compression. we apply the first
law considering thallhc system is llJl open system in steady-slate:

r
MI"-Q+W (1.16)

and the second law: Q ... T dS (1.40)

As compression is reversible and isothermal, we have:


Q=Ta5 (1.41)
W r = aH - Q = lJ,C T (1.42)
Calculations will be performed using the units provided in the diagram. In particular. we
nOle thai the h:mpcralures are expressed in degrees Rankine (OR).To COIlven 10 Kelvin:
T(°R) = 1.8· T(K) = 9("F) + 460
As the unit of energy is Btu/lb. we have:
llb",453.6g. I BIU",252'cal=10S4J and I 8tul1b:Z.J24J.g- 1
So. we arrive al:
T= 560"R
Q = 560· (1.55 _ 1.89) = -190.4 Blullb = -442.5 J. g'l
W = (1060 - I 100) - 560· (1.55 _ 1.89) '" 150.4 Blullb., 350 J. g_l
In order for the expansion \0 be reversible. it is appropriate to recover the work of
e~rmnsion. We will apply the previous Equation (1.16) to calculale this work. while
laking into account Ihat there is no exchange of heaL. and therefore:
W", lJ,H (J.4J)
for an adiabatic transformation
or: W = 990 _ 1060 = -70 Btullb = -163 J 'g-'
III reality. compreMion and expansion are irrcversible to a certain degree. and the val·
ues above represent the limits. Furthermore. compression is accomplished in 1'110 (or
more) adiabalic sleps. and therefore is accomrmnied by all increase in temperature.
Each increase is followed by cooling 10 restore the initial temperature. Thus the first
step can be substituled wilh two isentropic compressions going from atmospheric
pressure to 7 bar. and then from 7 to 50 bar. The calculation shows that in this ease the
work lhat must be provided is in the neighborhood of 400 J . g-I and lhe heat to be
released approximately -500 J . g~l.
Expansion may also take place wilhout recovering work. We would have Q = 0 and
W = 0 al the same lime. Expansion would therefore be isenlhalpie. With the help of
the diagram. we may verify thai it would nOi allow for ethylene condensation if Ihe
compression slep were not modified. and thatlhe compression should reach approxi~
malely 120 bar 10 achieve Ihe same rate of condensation.
17

o EXAMPLE 1.2
Methanol battery
The el«tromotive force of a methanol battery operating in an alkaline environment
al atmospheric pressure and under reversible conditions is theoretically equal to
1.33 V at 2.'i c c.
In practice. the following results were observed in the laboratory under the same
oondilions of temperature and pressure: a pOlcmial difference of 0.2 V and a heat
release of721 kllmal from oxidized methanol.
The reaction is described by the slOichiometry:
eliJOH +80W-6e --t COJ-+6H 10
3
"T0z+3Hp+6e --t 60H-

The rcactanlS and the products are in an aqueous liquid solution with the exception of
oxygen. which is gaseous.
These data allow us to determine the variations of the thermodynamic functions
accompanying the oxidation reaction. as well as the exchanges of heal in the case of
reversibility or free combustion,
Fi~l. we note that the variations of the thennodynamic functions will be the SlIme
regardless of the degree of irreversibility of the process. Indeed. the initial and Iinal
states are the same.
The work done by preso>ure can be easily calculated since the pressure of the sur-
roundings is constant

The variation in volume results from the consumption of OII:ygen. We apply the equa-
tion for the ideal gas state:
A(PV) '" RT Av
where Av denotes the variation ill the number of moles (-1.5 mol) and R
(8.3145 J'mol- I . K-l) denotes the ideal gas constalll. We lind that for a mole of
methanol oxidi7.ed: IV... '" 3.7 kJ.
Furthermore, we can calculate the elcctrical ellergy involved: If £ designah:s the
electromotive force. ?l Avogadro's lIumber (6.022 )( laD). e the electron charge
(e'" 1.6(2)( Io-l~ C). and An the number of clcdrons transferred. on the basis of the
preceding stoichiometry (All = 6). then:
IV' "'?l AntE" 964nAf,E

We thus rind thai IV' '" -no kJ in the case of reversibility (E '" 1.33 V) and
IV' '" -115.7 kJ from the rcsults observed (E =: 0.2 V). This energy is considered nega-
tive as the setup produces energy (electromotive force).
18 1. Principles. r1>",moop,amit: FuOCliom. "'" klNl Gis

By applying Equation (1.34) in a rcversible case. we de,;,'c:


t.G= W:'.. =-770kJ
at constant temperature
In the case of an actual working bancry. we firsl determine thallhc electrical energy
giyen off to the surroundings is effectively less than the decrease in the Gibbs energy:
-IV' < -6G. We can fUrlher group the energy exchanges: IV = 3.7 ItJ. Q = -721 kJ and
-W' = 115.7 ItJ. We can therdore calculate the variation of internal energy:

4U=W"t-W'+Q=-S3JkJ

from which we deri,'c the variation of enthalpy:


,HI = t:.U +6(PV)=-&J6.7kJ

and of the Helmhollz energy:

AA"'<1G -A(PV)=-766kJ
The entropy variation is derived from the values of Ii./{ and flG:

t.S-= MI-6G =-22371.K-1


T .
It is [rom this value that ,,'C can calculate the heal exchanges in the case of reversibil-
ity:
Q., T 4S .. --66.7 I;J
Finally. if there is no produclion of electrical energy (free combustion):
Q -" 4ft " -&36.7 kJ
Tablc 1.2 below summari7.CS these results (unilS: kilojoule. kelvin).

T." t.2
Variation of lhermodynamic pr~r1ies. heal e~changes.
and work during lhe o~;dalion of mel hanoI

Reversible Bauery E~perimenlal Bancry Fn::c CombU$lion


,u ..." ..." ..."

'".s ......7
-223.7
......7
-223.7
-<lJ6.7
-223.7

""
'G
-7'"
-770
-7'"
-170
-7'"
-no
Q -'<.J -121 ......7
W '-' '.7 '.7
W' -770 -ll~.7 0
19

1.6 THERMODYNAMIC FUNCTION: INTERNAL ENERGY, ENTHALPY,


ENTROPY, HELMHOLTZ ENERGY AND GIBBS ENERGY

1.6.1 Dependence on Temperature, Volume, or Pressure

Helmholtz energy. A. and Gibbs energy. G. arc. like inlemal energy. enthalpy. and entropy.
eXlensive functions. A change in each one of these properties allows us to judge the possi-
bility or impossibility of a transformation. in accordance with the conSlrainlS thaI are
maintained over tile course of Ihis transformation. l'hennodynamic equilibrium is related
to un extreme condition of any onc of tllese functions. It is for this reason Ihat lhe fune.·
lions may be called "thermodynamic pOlcnlials". It is therefore essential to kno.... their
variation as a function of the properties of the system.
As independent variables we wilt consider temperature, and either volume (for internal
energy. entropy. and Helmholtz energy), or pressure (for enlhalpy, enlropy, and Gibbs
energy), To arri\'e at the elemenlary variations of the thennodynamic funclions .....e will use
the fundamental Equation 123:
dU""TdS-PdV (1.23a)
Taking into account the dcfinition of Helmhohz energy and Gibbs energy (Eqs. 1.29
and 1.33) one may wrile:
dA ",,-PdV-SdT (1.44a)
dG=VdP-SdT (1.450)
or for one mole: da",,-Pdl1-sdT (l.44b)
dg=vdP-sdT (1.45b)
Since the internal energy. lhe Helmholtz energy and Ihe Gibbs energy are state func-
tions. and dUo dA. and dG. arc exact. total differentials. we derive the following equations
from them:
(;~), =(;;t
il 2A il 2A
Ihat is (1.46)
ilTiW = ilVilT
il 2G alG
ilTilP = ilPOT
Ihat is (;~), =-(;~), (1.47)

Similarly. we obtain the dcrivati\'es of internal encrgy and enthalpy as they relate to the
volume and 10 the pressure respectively:

U=A+TS gi\'es (au) _(aA) +r(as)


av,-av, av, and thus
(au) =r(aP) v_p (lAg)
ilVT ilT
and:

givcs (all) (aG) (as)


iJP,."" ill' / T ill' T and thus (all) (av)
iJp T" V- T iJT I' (1.49)

Wc hal'C already seen Ihat thc elementary variations of intcrnal energy al cunst3nt vol-
ume, or of cnthalpy al cunst3nt pressure as a function of temperature. was expressed. for.
homogenWU:!l mixlu~. using the corresponding heat capacities C" or C,. (Eqs. 1.8 and
1.14). The S.1mC is true of cuurse. for the elementary variations of entropy.

,m
20 1. Principks. ~icFunaions. I1>eIdNIGou

We list below (Table 1.3) the expressions for the thermodynamic function differentials
represented by TY for internal energy. entropy. and Helmholtz energy. and by T,P for
enthalpy. entropy. and GiDbs energy. These expressions do nol include the variable for
quantity of mailer. which must be considered for systems of variable oomposilion. They
will be given subsequently (Chapler 5). Since these equations 3fC all related to extensive
propcnics. if we apply them to a pure substance. or to a homogeneous mixlUre of constant
composition. these equations will be preserved while showing nollhe properl)' of the sys-
tem (u. H. oS; A. C. V). bUllhe molar property: u. h. .i, II. g. II.

Table I.J
Variation of thermodynamic functions with tcmpcralure and either volume or pressure

dU. CvdT T(:;)., J


+[ -p dV 0' ~ -cvdT + [T(:;t-/']d" (1.50)

dll .. Cl'dT. [v- T(:;)JdP 0' dh Hl'dT. [" - T(:;),.] dP (1.$1)

" (ar)
dS .. C.. _ . _
T aT ..
dV 0' w.. c....-:-
dT (ar)
• _
T a T ..
do (\.$2)

dT (,V) dT - ('0)
dS"C"T"- iJT,.d/' " dl'=c,.-
T- dP
aT ,.
(1.$3)

dAz_PdV_$dT 0' da=-Pd,,-.dT (I.~)


dG .. VdP-SdT dg,."dP-~dT (I.4S)
"
These equations are fundamental. Indeed. it is with the help of the deri..ati\'cs of the
thermodynamic functions with regard 10 volume or pressure that we shall arrive at the
"c1cviations from the ideal gas law", Here we invoke the Gibbs·Helmholtz equation
applied to Helmholtz energy and Gibbs energy:

,::'-
T
(';) .-If. " (1.54)
aT.. T-
,-'T ,
,G) ,G
(-2
aT
=_~ T
=H (1.55)
I' T
,-'-T ,

Their proof is very simple. For example. for the second equation we can write:
21

They should come close 10 a very common graphical representation in physical chem-
istry: we usc the variation of the logarithm of a value such as vapor pressure. the
liquid/vapor equilibrium constant, the solubility of a gas. the equilibrium constanl of a
chemical reaction. or the Talt constant. as a function of the inverse of absolute tempera-
HIre. In fact. for each of these valuC5lhcrc exists an equation relating it 10 the variation of
Gibbs energy.l!.G. accompanying the described phenomenon: Gibbs energy of condensa-
tion. of reaclion. or of formation of an activated complex. tiC. and the graphical represcn-
talion. allows us 10 obtain the variation of enthalpy. MI, of this same phenomenon.
This enthalpy variation itself is most frequently only slightly sensitive \0 temperature.
and Ihe graph obtained is linear.
If the variation of temperature causes a phase change or a cllemical reaction. it is then
no longer JlO5Sible to state thai dU v = C v dT or dH p = C p dT and il is neassary (0 intro-
duce Ihe ~Ialen(' heat associated with Ihis phase change or wilh the heal of reaclion. On
the other hand we may, willl the help of Equations 1.51 or 1.55. calculate the variation of
the heat of reaction or the Gibbs encrgy of reaction wilh the temperature. while pressure
remains constant, provided that tile systems fanned by (I) the reactan!$, and (2) the prod-
ucts. do not themselves undergo a phase change. We ....illthcn write:

(WI)
or ,"'C, (1.56)

a'G
RT M/
"-- (1.57)
a"-T ,
R

where AG and All are. respectively. Gibbs energy and enthalpy of reaction. and AC p rep-
resents tile dirference between the heat capacity or the products and reactants at constalll
pressure. taking into account the stoichiometry (see Chapter 13).
The heat capacities at constant volume and pressure are related. as are the internal
energy and the enthalpy. We may thus write:
dU= d(H - PV) = dH - PdV - V dP
which is to say Ihat by application or Equation 1.50:

dU = C"dT"t- [T(~~t-1'] dV = dH -l'dV - VdP

or: CvdT+T(aP) dV=dH-Vdl'


or,
If we are looking at an isobaric process. we would write:

CVdT+T(aP)
fJT v fJT
(av) dT=dHp=CpdT
f'

and thus: (1.58)


22

We can only use the derivatives at oonstant pressure or al constant volume by applying
the equations:

dP.(aP)
iJr v
dT.(aP) r ,Vi)V
and thus

0" dV=('V)
iJT
dT.('V)
I'iJp r
dP and thus

Thus is obtained:

(aP)' ('''''
C -C ;-T aT v =-T aTJ,. (1.59)
" (aP)
aV r
('V)
iJPr

1.6.2 Characteristic Functions

We return here to the particular role pl3)'cd by each of the functions thai we have defined:
the !iecond law may be exp~ !lSing anyone function from among them.ltttOrdinlllo
the colI.'ilfllinls .pplied 10 the s}'stem:
Internal energy. U: minimizlIlion at consillol entropy lind "ohlIne
Enthalpy. H: minimization 111 conslant enlropy lind pressu~
Entropy. S: mllxlmiulmn III constant internal energy lind "nlume
Ilelmhollz coerl,)'. A: minimization III conshmllempt'flIlure lind mlume
Gibbs energy. G: minimization al constant temperatun: lind prnsure
Furthermore. knowing one of thes..' funclions as II function of the variables thus relaled
to it. in fael provides aJlthe necessary informalion. We shall use lhe example of Helmholtz
energy.
If the function A Cr.Y) is known. one disposes also by applying Equalion 1.44 on the
pressure expressions (equalion of stale) and lhe enlropy as II function of these variables:

P(T'v) '" ~(aA) (1.60)


av "
S(T'v)=-(~; L (1.61)

and the internal energy. enthalpy. and Gibbs energy are obtained immediately:

U(T,V) '" A.;. TS =- A Cr.V) _ T{'A)


aT,
(1.62)

p'
23

II(T,V,=U.PV:A(T,V)-T(") _V('A) ( \.63)


aTVaVT

G(T,V) = A + PV", A (T,V) _ V('A) ( 1.64)


'V,
To obtain lhe heal capacity 3t constant volume. we can apply Equation 1.52:

C.> T(~ L
and thus. according to Equation 1.61:

(1.65)

Heal capacity al constant pressure is obtained from the heal capacity al constant volume
by application of Equation 1.59. which utilizes only Ihe derivatives ofprusurc e~pressed in
1.60. compared to volume at constant temperature or temperature at constant volume.
This calculation of all of lhe thermodynamic propenies from the characteristic funclion
A (T.V) may be used for olher characteristic fUnCliolU. G (T.P). for example.
In faci. more often than nolo we do not use the specified characteristic function as a
function of its own variables. but Tather Ihe equation ofslale P (T.II) or V (T.P). We may
also use the upression for the residual or configuration property that expresses the diUer·
enee between the characteristic function and the value thai this function would have if the
fluid were an ideal gas. As we shall see, these data (equation ohtate and residual property)
are equivalent. but insufficient in the sen~ that it is also necessary to know the variation of
heal capacity of the ideal gas with temperature.
Note thalaJllhe ~ng e.ttlluloos, ",Tilten for II system t'OnlainittlNmoles lIlnd inl'olv-
llllll", t:llenslve ".Iun V, U. H, S. A. C, C".etc..nuty be used fOl' molarVIII~~. U, 11., So etc.

1.7 THE IDEAL GAS

1.7.1 Equation of State and Thermodynamic Properties

It is important 10 recall the definition and properties of the ideal gas. Firstly. it represenls
the limit state of the real fluid when the density (mass/volume) approaches ~ero (often
misstated as whell pre!iSure approaches ~ero). It also makes up, as we shall soon see. a
cOllstant slep in evaluating the lhermodynamie properties.
In the ideal gas stale, the forces of intermolecular cohesion are null. and the effective
volume of the molecules is also null. Knowing this fact. the equation of state that will form
the definitive equation is especially simple. From now on. \Oo'e shall denote Ihe fluid proper-
ties in the ideal gas state by the e~poncntll, with N representing the number of molt'S. and
therefore would write:
PV' = NRT (1.66a)
24

or for one mole:


(l.(,6b)
R. the ideal gas constant, is expressed using the unit that is most appropriate to the cal-
culation being performed:

or.
R. 1.987 CIII· mol-I. K- I .. 83.145 bllr·anJ·mol- l • Ie-I. 82.058 111m ·anJ • mol-I·K- 1

If we apply the equations in Table 1.3. we end up with the results listed in Table 1.4 (for
one mole or ideal gas).

Tllbl~ IA
Varial;(m uf thermodynamic functions of Ihe ideal gas
wilh temperature /lnd either volume or prel'$ure

(1.67)

(1.68)

A.' _c..• _
.... dT . R d"
_ (1.69)
T "
do/'._RT d ,' ~~'dT da~ .. -NT din" (1.70)
"
dg"" RT dP
_ _ $' dT 0' dg~ .. -RTd t" P (1.71)
P

In this way. internal energy and enthalpy of the ideal gas depend solely on temperature.
The same is true for heat capacities at constant volume or constant pressure between
which e~;sts the Mayer equation:
(1.72)

But entropy. Helmh.olt7. energy. and Gibbs energy depend on bolll temperature and vol·
ume (or pressure). However. we nOIe the parlkularly simple formula Ihal relates Gibbs
energy and pressure. We know thai for ideal gas. pressure provides us wilh a convenient
scale of Gibbs energy. Several simple expressions of equilibrium conditions resull from
this equation: nolably Raoult's law for liquid-vapor equilibria. and Ihe Guldberg and
Waage law for chemical equilibria. where partial pressures playa role.
Thermodynamic propcrlies in the ideal gas stale are oflen related to an arbilrary refer-
ence lemperature Te• and a "slandard~ pressure of I bar. designated as po.
At this slandard pressure we can wrile:

hO(T.'>O) = hO(Te.PO) +fT c;(T.PO) dT (1.73)


'.
25

,'(T P')
P' dT (1.74)
T

and at pressure P:

h'( T.P) = hO(T.P") = Ii" (To.PO) +fT cp(T,PO) dT (1.75)


'.
I'
dT-Rln- (1.76)
P'

1.7.2 Heat Capacity

Ii is thus clear Ihal the properties for the ideal gas can be hlown as soon as we have the
va.lul.'S for heat capacity cp. We know Ihal the kinetic theory of gases yields particularly
simple results in lhe case of mono and diatomic compounds. Heal capacities are practically
inllarianl with temperatures close 10 5 cal- mol-I. K-l for noble gascs.and 7 cal, mol-I. K- l
for diatomic compounds under ordinary conditions of temperature. For more complex
molecules. heal capacity depends on the nature of the compound in question and on tern·
perature. In this calculation. we must take into account the rotational movement of the
groups composing the molecule (and possibly tlie barriers to rotation). and the longitudi-
nal and transversal vibrations or the interatomic bonds. This calculation is supported by
spectroscopic data. II generally results in complex expressions that are dirficult to intc-
grate (which is a major inconvenience when calculating the variations or enthalpy and
entropy). and it is generally prererable to apply more empirical equations that permit us to
obtain the results or rigorous CllIC'Ulations with all the precision required.
Polynomial expressions:
("~=II+bT+("Tl+dTJ+... (1.77)
in which a, b. c. If are empirical variables dependent on the component under examination,
are quite orten used. However. it is advisable to avoid all extrapolation beyond the tem-
perature range for which these expressions have been formulated. a range that should be
known. In general. they may not be used at low temperature (below 2S'C). Therefore. the
expression proposed by Aly and Lee [1981) is preferable:

c"=B+C [ On' ]' +E [ Fn ]' ( 1.78)


" sinh (DIT) cosh (FIT)

The expressions corresponding to enthalpy and entropy are:

[
hO(T) = 1I0(To) + BT + CT T0coth (0) P tanh (P))'
T - ET T T T- ( 1.79)

SO( T) = SO( To) +

{Bin T+c[ ~ coth (~)-ln sinh (~)]-E [; tanh ( ;)-In cooh (;)]}: ( 1.80)

26

III these equations, B, C. D. E. Fare the empirical coefficients tl1al depend on the nature
of the compound in question.
As an example. we can also cile the formula applied by YoungIO~'e and Ely 119811 to the
calculation of heat capacity for light hydrocarbons (methane. ethane. propane. n-butane.
and isobuI3nc):

G,
where 1/: - (1.81)
T

1.7.3 DataTables

The literature supplies the values of thermodynamic properties for a large number of pure
substances in the "standard" stale. lhal is. for most substances that we encounter. in the
ideal gas slale,and 311lle standard pressure of one bar (0.1 MPa). The principal exceptions
are carbon. which is in the graphite state. and sulfur, whose state varies according to the
tables.
These properties are oflen supplied for a number of temperature$, and al least for
298.15 K. They contain molar heat capacity. enthalpy. and entropy. For enthalpy. the start-
ing point is arbitrary: sometimes we find the values for h~ - h"o. that is. the enthalpy rda-
tive to a tcmperalUre of 0 K. Any other starting point is acceptable. For entropy. most of
the tabh..-s adhere to the ~third law of themtodynamics". or to the Nemstlheorem. accord-
ing to which ~the entropy of any pure. solid. crystallized substance is null at absolute zero",
There is no disadvantage in selecting an arbitrary starting point as long as the calculations
arc not for a chemical reaction (see Chapter 13).
Such data. for a "ery limited number of compounds. are found in Appendix I.

REFERENCES

General Works
Ben KE. Ro... tilUOn JS, Saville 0 (1975) TIr~mwdJ"u",ics for ChtHlku/ £ngi_rs. lhe i\11!.1onc
Press. LonOOn.
Canen HB (I 'l6O) TnUmQ<I)"IWHlia. .Iolln Wiley and ,;ons. New York.
Dodl! M (I \156) Buses {llm/"mell/uiu tl upplir"lim,s dt IIJ Ihumt><JJ""",iq"t rMmique. Soci<!I~ d'&li·
lion d'cl\$<"ignemenl supl!rieur. Paris.
Modell MM, Reid RC (1983) Thw"(H/}'",,micsat1d Irs AppliclJ/iOtls. Prentice·llali. Englewood Oifrs.
Newkney.
~neloult A (1992) COW'i' I/t TlrumlH/J"umique. Uni,·e~i.~ d' Aix·Marscille.

Specific References
Aly FA. Lee LL (t98\) Self OOI1sistent equations for cakulaling the ideal gas Ileal capacity. enthalpy
aoo enTropy. FI..iJ PhlJM EquilibrilJ. 6. 169-179.

p'
27

Canjar L.N. Manning FS (1967) Thm",xlynllmk ProptmiQ lind ReJuud Corrf'l/Jlirms 'QrG/Uts. Gulf
Publi,hing COTpOflItion. U0U5ton. Tuas.
Younl1,lo~e DA.
Ely JF (1987) Thermophy"ical propcrlics (If nuidL II. MClh.llnc.\:lh,.,.",. Prtll"'''''. i...r
bu18"" and normal bulallC.J. Ph,S. Chtm. Ntf DiJ./Il,16•.111-797.
I
2 Properties of Pure Substances

The equations presented in the previous chapler show that the dctennination of equilibria
or of energy balances implies the evaluation of lhennodynamie propenies.
Due to the existence of intermolecular cohesion forces. the calculation of these proper-
ties in the ideal gas slate is only a firsl step. Since the systems we deal with in real life are
themselves mixtures. a knowledge 3ml un<Jen;landing of the behavior of pure substances is
itself but a seoond step. and generally an essential onc. To study the behavior of a mixture.
we often apply simple rules of weighting to the properties of its components. Any impreci-
sion during this second step inevitably affects the final result. For example. we cannot hope
to correctly calculate the liquid-vapor equilibria of m;,[lUres if the vapor pressures for pure
substances are in error.
Although sometimes merely a review of well known information. knowledge of some of
the values is almost indispensable to applying the methods that will be developed later on.
To a ccrtain extcnl. these yalues make up the minimal"database" that. although limited.
nevertheless allows us to understand the thermodynamic properties across a wide range of
temperature. pressure. and composition. They are th~ crWeal pobtt~ VJlpot' pruSUIT. alWl
heat or VJlporizalion.
We also stress the continuity that exists b<eht"ftn the liquid and ps statn. This continu-
ity warrants, sometimes even imposes.. lhat the same calculation methods be applied to
these states: it helps to understand the behavior of fluids at high pressure thaI we some·
times find extraordinary.
[n this chaptcr. wc will repeatedly point out deviations from the ideal gas laws. For
properties such as volume or lhe thermodynamic functions. we ....ill gather the expressions
that relate these deviations and allow us to calculate them.

2.1 THE RELATIONSHIP BETWEEN PRESSURE, VOLUME


AND TEMPERATURE. L1QUID.VAPOR EQUILIBRIUM

If the distance between molecules is very IMge and lhe molar volume approaches infinity.
the cohesion forces become negligible and the properties of tile real fluid approach those
of the ideal gas. llte first step with calculation of the thermodynamic properties of the ideal
gas is then a reasonable approximation for gases at low pressure. The extent of the range of
30

application depends on Icmpcrallire. and of course on the desired pre'Cision,as we shall sec.
lt is thus in p~lrticular allow densit)" thai the pressure tends toward the value calculated for
the ideal gas and that. regardless of temperature. the ralio P"IRT approaches I:
RT Pu
if ... ...;.",> then P-+- or _-+1 (2.1)
" RT
This does no! mean thaI the difference belween the molar volume of the real Iluid and
the molar volume of the ideal gas cancel each other OUI. When the molar volume
approaches infinity. the value limit of this difference is not zero. It is called Ihe second vir-
ial coefficient, and increases from very negative values at low temperature to low. but pos-
itive values at high temperature. as shown in Table 2.1 and Figure 2.1. Knowing the values
of the second virial coefficient allows for an eXDe! evaluation of the thermodynamic prop-
erties at low density. These values were the subject of compilations [Dymond and Smith.
1980] and of prcdicti\'e correlations that we shall discuss later (Chapter 3).

Table 1.I
Variation of the second vinal rodficient. B. of ethne with tcmperalUre (units: on)' mol")

T H T H T H
(K) (K) (K)
173.15
198.15
-539
-<08
""IS
373.15
-IJO
-112
573.15
623.15
-"
-"
223.15 -321 3911.15 -'¥I 673.15 -IS
248.15 -2"' 423.15 -'" 723.15 -<I
173.15 -215 448.15 -73 773.15 -2
19S.15 -u" 473.15 -oJ 823.15 J
32:l.15 -1S2 523.15 -<7 873.15
"
By following. at constant temperalUre. the evolution of the pressure as a function of vol-
ume for a given quantity (one mole for example) of a compound. we can qualitatively
characterize the different ranges of ..the pressure. volume. temperature space" and deter-
mine certain characteristic properties such as vapor pressure. molar volumes of Sllturatcd
pha~s. and critical points.
Let us consider the case of ethane. for example (Rgs. 2.2 and 2.3. Table 2.2). When the
system is homogeneous and if the amount of matter is known. two variables. sueh as tem-
perature and either pressure or volume. are necessary 10 determine its properties. At 2WC
(293.15 K) and 01 atmospheric pressure (0.101325 MPa).elhane is in a gaseous state and
the occupied volume is close to 23861 em)· mol-'. a value slightly less (24054 em)· mol-I)
thlln the volume obtained by applying Ihe equation for the ideal gas. The Mcompressibility
factor" defined by the equation:
Z .p.,- . -
" (2.2)
RT v'
is slightly less than one. We state that "the deviation from the ideal gas" is negative, aileasl
as regards the calculation of the volume. It is the result of intermolecular allraetion forces.
which will be more pronounced if we decrease the average distance between the mole·
31

010,------------,

-300

roo ..
_+----,-----,----,---..J
IlOO
Temperature {K}

2.1 Variation of the second virial """ffi<;ient of


~lll'"'
elha~ with temperature.

cules. Indeed. when we decrease volume and increase pressure. the compressibility factor
decreases. We follow on the 293.15 K isotherm in Figures 2.2 or 2.3 the curve AB. When the
pressure reaches 3.76 MPa and the molar volume 345 em J · mol-I, we SCI: thai a morc dense
phase appears. the liquid phase. We speak of II ~dew" poii'll. The state of the system is rep-
resented by point 8 with coordinalell "v." and P" on Agure 2.2. and P" and Zl~" on
Figure 2.3. point C with coordinates vl.. a (88.3 cmJfmol) and P" on figure 2.2. and P" and
zL,a on Figure 2.3 corresponding to the liquid phase. If we continue to decrease the vol·
ume. Ihis liquid phase will accumulate at the expense of the vapor phu.se. The equilibrium
condition reduces the number of indcpendcnl inlcnsive variables. The specific or molar
volumes or each one or lhe phases 111(" and IIl,a as well as pressure P" will remain constant
for the duration or tbe condensation process. This pressure, maracterislk ror. pure sub-
5tmee in. 51.le or equilibrium belwecn tbe 11m pltast$ or liquid ancl VWlpot.1s called ".pot
p~re. Representative point M of lbe belerogcneous system will lie on segment BC of
Figure 2,2. marked by pressure P", and lhe molar volumes of the equilibrium phases ll'~"
32

'."---00

,
P, ------ ,, • --,
303.15

,f 4.5
,,•
> •

j•
298.15


• ,,
T .. 293.15K
C

o "00

Rguno l.l
_ : isoIhem,,; : Iwo-pha5e envelope: *:critical point.
Pl'cssure. .'olul"lX.tcmP'C'raHlrC diag11lm for cillane.

0.75

I;:
~O.5
,•

~ c
--- - -- ,
o
" Pressure (MPe)

RI""' Z.J Variation or thecomp..,..ibility facH>f ror clhane with


preilSure and temperature.
- - - , oo'hcnTl$: ---. -: two-phase: envelope: *
:critical poinl.

k
33

Table 1.1
Volume";'" propenies of eth~ne

T.293.ISK T.298.1 K
P(MPa) .. (cml·mol-') Z P(MPa) u(cml·mol- 1) Z
0.990 24278
0.101325
3.1634
3.7634
"'''
'""82'.. 0.533
0.136
0.101325
4.1876
4.Hn Ii '""
0""
0.478
0.160
,.s
r .. 303.ISK
0.186
" "
r. J05.)4
0.193

') v{c;ml. mol-')

...'"
P(MPa) II (cml·mol Z P(MPa) Z
0.101325
4.6508 " 0.993
0.397
0.101325
4.8714
"877
14S.3
0.993
0.279
4.6508 107.9 0.199 4.8714 14S.3 0.279
S, 0.212
" r.308.ISK
93.6 0.""
"
P(MPa) v(cm l 'mol- 1) Z
0.101325 2S III 0._
'.s 513.8 0.700
'.S 316.9 0.55'
" 101.6 0.262

and ,,1..", and 'heir compressibility factors Zv... and ZL... of Figure 2.3. For a volume bal-
ance. we can know the proportion of each of the phases by:
v _ vL." z_zL... eM
--:
"Va _ V LO" '" ZV.,,_zL.. "" CD
(2.3)

This equation is expressed by applying the lever rule to segment BC of Figures 2.2 or 2.3.
The last trace of vapor phase disappears when the volume is reduced \0 a value of 11-"
(88.3 cm'/mol). We may then speak of a ··bubble·· point. II corresponds to point C with
coordinates "I.,,,
(88.3 cml/mol) and P" on Figure 2.2. and P" and ZI.." on Figurc 2.3. If wc
continue to dccrease the volume. sincc thc liquid phase is not very compressible. the pres·
sure rises rapidly (CUI"YC CD on Fig. 2.2) and the compressibility factor of the liquid phase
is practically proportional to the pressurc (curve CD on Fig. 2.3). At a higher temperaturc.
298.15 K for example. the change in the system state and in the pressure is qualitatively the
same. However. we observe that vapor pressure is higher and that the difference between
the properties of the two equilibrium phases diminishes; densities approach each other
and the liquid phase becomes more compressible. BeyOild 305.4 K (al 308.15 K for exam-
ple) and regardless of the volume. we cannot dete<:t a phase ehange. and pressure increases
in a regular fashion (curve B'D' in Figs. 2.2 and 2.3) when the volume is decreased. The
temperature above which the phase change phenomenon disappeaR is called the critical
temperature. 305.4 K in the case of ethane. The .. thremoJd of collCleaslltion"" is then
~u«d 10. point of inflmion...hieh ili ailed the mtieaJ point. The coordinates are the
critical volume v~ and the critical pressure P<. The poinls represenling saturated vapor
J4

phase Band $lIturated liquid phnsc C describe the two curves of the "two-phase enve-
lope". These curves are joined tangentially al the critical poilil.
Through the "critical ronstraints":

(aP) (ii'P)
ilvr""a'llr"'O
(2.4)

knowing lhe Te • P,_ and vr coordinates oflen will allow for the identification of the vari·
abies of the equation of stale (see Chapter 4). We will need il to apply the pTedictive corre-
lations based on the corresponding Siales principle (see Chapler 3). For Ihis reason. lhe!;e
dill. mllY be considered characteristic prupertift urIbe rompooe.ts and put inlo any data-
base. They are not always accessible to experimental determination. Therefore in paraffin
hydrocarbons wilh a high Illlmbcr of carbon alOms (grealer than approximately 16) the
phenomenon of thermal decomposition hinders their determination [Tcja. 1989]. They arc
then calculllled using structure correlation properties (Chapter 3). or from other measura-
ble variables such as boiling temperature at atmospheric pressure. or density. Without
physical reality. the critical points in this case represent only characteristic parameters
related to the correlations that produced them. and 10 the models that make usc of them.

2.2 VAPOR PRESSURE

2.2.1 Liquid and Vapor States


The .'apor pressure curve is limited at low tempemture by the triple point that represents
the conditions at which the solid. liquid. and vapor phases cocltist, and by the critical point
at high temperature.
Figure 2.4 shows the vapor pressure curves for lhe alkanes from methane through
decane. for carbon dioxide. and for methanol. Note that the hydrocarbon critical points fol-
Iowa regular variation with the number of atoms in the pamffin chain. at least above
elhane: increase in critical temperature. decrease in critical pressure. We also note that the
critical pressures or more polar compounds (carbon dioxide hu a quadropolar structure).
or compounds autoassociated by hydrogen bonding such as methanol. are clearly higher
than lhose orthe hydrocarbons. The critical point for waler is: T. = 647 K. P, = 21.7 MPa.
Familiarity with the vapor pressure curve helps evaluate the states or mailer. liquid or
vapor in particular.
Identification is. however. not wilhout ambiguity. For example. if we have a pressure
between the triple point pressure and lhe critical point pressure at a temperature lhat is
higher than lhe melting temperature. a rise in temperature will allow us to observe the
phenomenon of vapori7.ation. We will have then correctly identified the corresponding
ranges pertaining to the liquid and vapor states. On the other hand. if the pressure is higher
than lhe critical pressure.....'e will then detect no change or phase. and the attribulion of
qualifiers and limits to the ranges involved is subjective. It is the same for isothennal com-
pression according to whether it lies above or below the critical temperature.
II is useful to recall lhe experimenl lenned "critical point lour~ shown in Figures 2.2
and 2.5. Depaning from point B chamcteris:ticofa Slltumted vapor (forethane. po ~ 3.76 MPa.
J5

",-----------------------,

.co,
,
,
,
,
,
c, ,, e,
,,
,,,
,
,
,
,,

t'lpn: 2..4 Vapor pressure C\Ir.-es and crilj(,al points (*) of paraffins
C 1 - C 10 ' of carbon dinxide. and Qf methanol.

"v..... 345 cmJflTlol), 11\ a temperature of293,15 K and constant pressure. ....e increase this tern·
perature to 3011.15 K (path 88').&nd then al constllnltcmperalure ....e COITlpn:5S the system to
a pressure higher than the critical pressure along 8'D'. We then return 10 the initiallcmpera-
lure (293.15 K) at constant pressure along 0'0. and. lItlhis temperature. decrease the pre!;-
sure to a value e<juallo the vaporprt."SSun: (P"= 3.76MPa) along DC. We find ounelves 31th.:
saturated liquid state (~" '" 883 cmJlmol). Along this path BB'D'DC we never crossed tnc
vapor pressure curve. btll nevertheless went from the saturated vlIpor state \0 the satlJrnted
liquid slale. We must oondudc thallhcrc is continuity oct""CCIl the ''''"0 Slates no mallcr how
mark.ed the: property dirfcren«s such as molar volume are. or how natural the distinctioo
between liquid and vapor is along the vapor pressure cun·e. As we have seen. these property
differences decrease when temperature increases. and disappear at the critical point "'here
liquid and vapor are identical. We conclude bf saying that this distinction betwl.-en the liquid
and vapor states makes sense only if both stmes coexist.
We must also point out certain features of the homogeneoUJi fluid phase within the crit·
kal :tone. As shown in Figure 2.2. the molar volume varies "cry quickly with pressure or
temperature. It is also the case with molecular interactions as well as with some thermody-
namic properties such as enthalpy. Under these conditions. fluid. while remaining homoge-
neous. demonstrates intermediate properties between the liquid and vapor phases and its
properties arc particularly sensitive to relatively smallltariations of temperature and pres-
sure. Among these properties is solltent power. put to good usc in supcrcritical soh'em
extraction. We also know that it is particularly difficult to evaluate accurately within this
zone certain propcrties. such as heat capacity for example (see Chapter 4, Fig. 4.3).
36

.-.-----------,
Dr- - - - - - -eD'

, -1---.-----.------1
'"" 300
Temperature (K)

The vapor pressures of the most common hydrocarbons and a large number of com-
pounds have been detennined. and the results have been collected in many databases such
as the ones assembled by Reid it al. 11976. 1987]. Daubert and Danner /1986]. or Boublik
ttl 01. [1984J. However. for CQrnpounds with large molar mass, in particular of heavy hydro-
carbons. experimental data are scarce and sometimes inaccurate. A real effort is being
made to determine them. motivated by the problems posed in calculating the thcnnody·
mimic properties of petroleum nuids.

2.2.2 Vapor Pressure Equations

2.2.2.1 Clapeyron Equation


Applying the equilibrium condition allows for the derivation of the Oapeyron equation.
The transfer of dll moles from the liquid phase to the vapor phase is ac:oompal1ied by a
37

variation of Gibbs energy equal to + gv... lin for Ille vapor phase, and -r"
dn for the liquid
phase. TOlal variation. which must be zero by virtue of Ihe equilibrium condition. is wriuen
as:

anllhus: (2.5)

Nole Ihat the change of phase happens without discontinuity of Gibbs energy contrary
to whDt we obser\'c for volume or enthalpy. Furthermore, the enthalpy and entropy varia·
tions accompanying vaporization are related: if 81(" '" then: 11-''
(2.6)

This equation between lhe enthalpy and entropy variations DlX(lrnpanying the phase
change has already been used in the previous chapter in Ihc uample relating to a lique-
raclion cycle (Eq. 1.37).
Equation 2.5 remains valid as we move along the liquid.vapor equilibrium ClIf\'C. The
variations of vapor pres:;ure dP" and temperature dT are themselves related by the equa-
lion:
d(g v... _ gL.,,) '" 0

or by the application of Equation 1.45:


(li v... _ 11 1-") dP" _ (sV." - .1"1.") dT '"' 0

dP" .l"v.,,_.I"I."
or. -d-T- • C,",o--',C1:c,o (2.7)

and by taking into account Equation 2.6. we may substitute the variations of enthalpy for
the variations of entropy, that is 10 say the heat of vapori7..ation M":
dP" /rV,"_hL." M"
- '" = (2.8)
dT 7'( v v."-v'-") T(VV."-Vl~")

The Clapeyron eqllllti(HI thllt we blll-ejUSC delhed emboclift 1M) Ipprolinudon whlltso-
el'er; it is a simple and especially important example of equations that thermodynamics
imposes on properties such as enthalpy. volume. and equilibrium eharac'leri7.ation.
However. it invol\'es a differential equation whose integration requires. at least in princi-
ple, knowledge of variables (heat of vaporization, molar volume) that are more difficult to
acquire Ihan vapor pressure itself, It is therefore applied with the help of restrictive
hypolheses and results in empirical correlations.

2.2.2.2 Empirical Correlations


A large number of equations have been proposed to express lhe change in vapor pressure
with temperalure. They differ in lhe extent of the range CQ\'ered, their ability to allow for
accurate extrapolation outside the range (in particular to low temperatures), their theoret-
ical basis. and of CQurse their complexity. It is not within the scope of this text to present an
exhaustive review of all of them; we will provide but a few examples.
3.
The Clausius-Clapeyron Equation
In order 10 integrate the Clapeyron equation. we may consider the molar volume of the
liquid phase to be negligible compared to tllal of thc vapor phase. and llial the vapor phase
behaves like an ideal gas. We am,'c at Ihe expression:
dP" "'hIS
dT = RT2
P"

or: (2.9)

[f we funtler assume thai the heal of vaporization is constant, we can then integrate the
preceding equation and obtain the ....·ell known form:

(2.10)

Ihal may be effect;"cly applied to the calculation of vapor pressures in the neighborhood
of the boiling temperature at atmospheric pressure.
More generally, \I'e can wrile:
B
Inl""=A+_ (2.11)
T

where the values of A and 8 arc considered variables adjusted to experimental data and
may depend on the range of temperatures under examination.
It is intercsting to note that the graphical representation suggested by the Equa-
tions 2.10 and 2.11 is in fact applied to a ,'ery large temperalure range. Figure 2.6 shows the
change of vapor pressure for ethane and methanol between the boiling temperature (T~)
at atmospheric pre~'Sure (P~) and the critical temperature. We observe that the experimen-
tal data are found. with reasonable approximation. on the straight line of the equation:
I I
---
T T.
(2.12)
1 1

Table 2.3 allows for a comparison between experimental aJld calculated values. We note
lhat inlerpolation of the calculation yields results of alXcptable precision. Yet. below the
normal boiling temperature. error increa~ rapidly due in part 10 the extrapolation. and in
parlto the fact that the errors are evaluated as relative value!.. Figure 2.7....·here the devia-
tions between experimental interpolated values have been deliberately exaggerated.
demonstrates this phenomenon. Wc maintain that the expression 2.12 should not be
applied eXlXpt for interpolation.
39

-,
, , .
1 OOOo'l'lK}
, , ,
Fipu U Variation of the Iog:lrilhm of vapor pre5Sure forelhane
and methanol as a fUDClion of the in~erse ofabsolule temperatun:.

Table 2..)
Vapor p~ure for ethane and methanol. Calculation by interp<:>l.ation between
the boiling point at .'m()lpberie pressure and the critical point (ApPlication of Eq. 2.12):
elClrapolalion 10 low temperatures: oompari5Oll "'ilh upenmental dal.

Ethane Methanol
T p••
(bllr)
p~
(bar) ,,,,
fj,PIP T p~
(bar)
p~
(bar) ,,,,
"PIP

"'J
\00
\20
\"
\«)
O.(lX){lll
O.lnlll
0.0035
0.038
0.214
OJXX1OJ7
0.00025
0.0052
0.0.15
0.225
..,
22J
\30
\7
257.7
273.15
293.15
313.1S
323.15
0.0133
0."
0.1275
0.3509
O.55l3
0.018 S
0.00117
0.1421
0.366 \
0.>62 ,
J9
\9
\\
'.3
2
\., 0.79 O.7~ 0.111 333.15 0.11397 0.8419 0.26
184.6 1.01325 1.01325 0 337.9 1.01325 1.01325 0
\'"
200
D·H
2.174
UJ8
2.154
-<l."
4191
343.15
353.15
1.243
\.'"
l.2Jl
1.762
-O.9S
_1.8
2\0
220
3J<l
4.922
3..313
4.9005
-<l.'
-<l.~
373.15
393.15 ""
'.396
JA'"
,\«)
_3.45
-3.66
no 7."" 7.001\ 0,02 413.15 10.88 10.52 -3.33

""
270
13.01
22.\
13.14
22.45
,,.,
.15."
\
\.,
433.15
453.15
21.95
27.14
2\.43
26.61
-2.35
-1.95

'" ."
300
35.14
43.54
\.41
0.75
473.15
493.15
40.43
".~
39.91
57.91
-1.30
-<l."
301.'
'" 0 512.6 ,\ 8\ 0
40

-. 1----r---,----,--"'-I
3 • , ,
1 OOCVT(K)

~'p ... 1.7


Variation of lhe logarithm of elhane "".pot" pressure 15
a funClion or the inverse of absolute temperalUre (the deviations
from linearity have been exaggerated).

Tab'" 2.4
Cakulation of vapor pressure by linear interpolation between
the boiling pOlim at atmospheric pres!lllrc and the critical point

Error{%) Error(%)
Compound Compound
Average Maximum A>'C:f8ge Mu;mum
Mclhaoo
,U 2.7 Cydohcxanc I." ,.,
Elha"" '.6 IJcnzen<:: ,~,
2.7
Pro~ 0.'" '.7 Toluene 1.10 2.2
,,-BUlane 0.94 U Methanol 2~7 3.7
lsob"'tane
/I·Pentane ,I., 3
2
Elha",,1
Acetone
4.26
2.11
7J
4.'
",UeulI(:
,,·Hcplane
1.46
1.28 ,.,
3.' Carbon DiOKide
Iiydrogcn Sulfide
0,.
3.32
0.'
U
/I·Octane L61 • Water V '.6
41

Thblc 2.4 shows the average errors obtained for some compounds. always using interpo-
lation. between the boiling temperature al atmospheric pressure and the critical point,
However. il is quile evidcnllhat none of the three approx.imations used above 10 derive
the Oausius-Qapeyron equation is valid within such a wide temperature Illnge. As we
approach the critical point. the molar ~'olume of the liqUid phase ;s nOI negligible com-
pared to thai of the vapor phase since they both CQnvcrge loward II common value. The
vapor phll5e deviatcs significantly from the behavior of the ideal gas, ll'J shown by the val-
ues in Table 2.2. Finally. the heal of vapori7..illion decreases steadily toward zero. In fact. the
linear correlation obtained results from the compensation between dcYiatiOll5. and il is
only valid if vapor pressure is low and Ihe temperature range is narrow.
If we denote by /!Z" the difference belween the vapor and liquid compressibility factors
at equilibrium:
I!Z" = Zv." _ Zl." (2.13)

the Oapeyron equation (Eq. 2.8) can then be writtcn:

dln(P")
I
.--- "".
R tJ."
(2.14)
d-
r
The eJl;perimental data show that the ratio t:Jr"'/!Z" varies linle with tcmperalUre.
which explains the near linearity of the vapor pressure ploued against Ihe temperalure
when using logarithmic scalcs of In (P) and 1fT. We sec here an cum pie of simple and rel-
atively precise "correlations" arising from a fortunate coincidence of imprecise hypothe-
ses. Then: arc other. less obvious ones. In this panicular case. it would not make $C!lSC to
derive the heat of vaporization from the slope of the line represented by Equlltion 2.9.
since it would be necessary 10 determine the lemperature to which this quantity corre-
sponds.

The Antoine Equation

If we limit ourselves to a relalively narrow range.lhe Antoine equation:

10glQ I'" '" u _ _ b_ (2.IS)


,,8
(where 6denOlCS the lemperature). can achieve excellent precision: the variables II. b. care
specific to the substance involved. It should be emphasized that. according to the authoT$.
the units of temperature. pressure. and the logarithmic base will vary.
As an example. Table 2.S shows the values of these variables for several compounds
[Boublik, 19841. They have been determined from experimental results covering pressure
intel'V1lls. which vary according to the nature of the substance in question. yet arc alwa)'1i
ncar atmospheric pressure. The use of these data ;s not recommended if the vapor pres-
sure is not in the inlerval of 20-200 kPa (0.2 to 2 atmosphcre!!I). Other very eJl;tensive tabu-
lations of these variables can be easily found in the literalUre IReid elll/.. 1987: Yaws,
1989].
· ,IU'

an , d
4J

b
cyclohexane : In p<1"Q---
« •

benzene: Inpa",d--- •
f+'
The equality of the vapor pressures would mean that:
(0 _il)OI + [(a-d)(c + f) -(b -~)18+ (a- d~f + «-bf=O

The numerical values of the variables /I. b. ... f lead to IWO solutions: 9 '" -18900C
and 9 = SO.84°C. Using this second solution. the corresponding vapor pressure is
37.35 kPa.
Of CQurse. we must allow for the uneertainly of the valucs arrived al in this way. E\'cn
so. the inversion of the vapor pressures of cyclohexanc and benzene at about SO"Ccan
be taken as certain.
The poilU of intersection of the vapor pressure curves of \1"0 compounds is kno.....n as
the Bancroft point.

The Frost-Kalltwarf Equation


Without adopting the very restrictive hypotheses lhal led 10 the Oausius·OapeyTon
equation. we can consider Ihat the molar volumes of the liquid and vapor phases at satura·
tion olxy the van der Waals equation of state (see Chapter 4). and that the heat of vapor-
ization is a linear function of thc temperature. We then arri\'e at the expression [Harlacher.
197°1:
8 po
InP":A---ClnT+D - (2.16)
T T
The parameters of this equ3tion. while oonn~ted in principle to those of the van der
Waals equation of statc and to the heat of vaporization, are in fact determined by regres-
sion from experimental data. Their valuC$ are given in the work of Reid ~I al. [1987]. Their
numlxr can be reduced if we make the equation pass through lhe critical point. or lhrough
the boiling point under atmospheric pressure. These possibilities havt: been examined
quile recently by Rogalski ~I al. [19911. who propose scvcral methods of prediCling these
parameters in the case of hydrocarbons.
The (act thai this equation is nOI explicit in either pressure or temperature is a minor
disadvantage.
When studying the problem of calculating vapor pressures at low temperature. we may
havt: to perform a more rigorous analysis of the variation of the heat of vaporization with
temperature. This analysis sheds light on the heat capacities of the liquid and of the vapor
at SlIturation.ll has been developed by King and AI-Najjar 119741 and applied by Ambrose
[19801·
44

The Cox Equa!ion


Thi~ equation has only three parameter.; thai need to be determined from experimental data.
bUI it also assumes that the boiling point T~ at atmospheric pressure is known. II is wrillen as:

In ~ =(1- :;)eXP(AO-l-AtT+AzT2) (2.17)

Ruzicka and Mayer [19941 recommend il for representing the vapor pressures of hydro-
carbons.

The Wagner Equation


The precision wilh which experimental datil can be interpolated by various npressions
has been investigated by Ambrose 11978aj. Given the number of variables thai need to be
determined. preference is given to the expression proplXSed by Wagner 119731:

III po .. Tr(Ar+8rl~+CrJ+Dr6) where r=I-:!... (2.18)


~ T ~
The qualities of Ihis same equation wtlen extrapolating to elevated temperatures and
when calculating the critical pressure. have also been studied jAmbrose. 1978bj. The
numerical values of the parameters are set out in the work of Reid ef at r19871.

2.3 ENTHALPY DIAGRAM AND HEAT OF VAPORIZATION

2.3.1 Dependence of Enthalpy on Pressure and Temperature

In order to present the change in enlhalpy of a pure subslance with pressure and tempera-
ture. we shall make use of the enlhalpy diagram for ethane (Fig. 2.8) and describe it along
several isobaric paths. The variations in enthalpy then correspond to the quantities of heat
absorbed by the system along these paths (Eq. 1.13). We note first of all that the enthalpy
is evaluated only with respect to an arbitrary origin (Chapler I). This origin can be the
enthalpy in the standard Slale at a temperature of 0 K.and we would then consider the dif-
ference h·r-Ir~. More commonly. we win choose a "reference enthalpy." such as that of the
liquid at its boiling point at atmospheric pressure. Finally we must recall that. since the
choice of the origin remains open for each of Ihe constituents of the system under consid-
eration. it can be adapted to any applicalion. but obviously it cannot be modified during
the course of a given computation. It should also be recalled that the numerical values of
enthalpy cannol be compared without considering the origins selected!
At a pressure below the critical pressure and staning from a temperature where the
nuid is unquestionably in the liquid slate (point A. T,. 285 K. P '" 3.76 MPa), we can dis-
tinguish three sections along an isobaric varialion. which can be found in Figure 2.8: curve
AB represents the change in the liquid from 285 to 293.15 K. segment BC (T,. 293.15 K)
pertains 10 vapori:t.alion at the partieular pressure. and finally curve CD represents the

p'
45

12.5
P.O.l MPa D

3.16

----------

,,,
'" '" "'"
T&r'I1P"rature (K)

''C''''' U
Enthalpy diagram for ethane.
- - : isobars: - - --- : two-phase envelope: >I< :crilical point.

change in the vapor between 293.15 and 315 K. Using Equlition 1.14, (he variations ;n
enthalpy can be evaluated as a funclion of the heal capacilies of lhe liquid cf.of vapor Cf.
and of the heal of vaporization M". Several isobancan thus be lraced. nOling lhat the pres-
sure has little influence on the enthalpy of Ihe liquid. at [easllls long as the lemperallJre is
well below lhe crilicallemperalure. and these isoblln; are practically the same in Ihe liquid
range. By connecting the poinls representing the liquid and vapor phases al saturation, we
.race IWO curves which meet 81 the critical point. and which constitute the Mlwo-phase enve-
lope~ on Ihis diagram. It corresponds. poirll by point, to the two-phase envelope drawn on
the preSllure!volume diagram (Fig. 2.2). Although they describe the variation in enthalpy
with temperature. the slopes of the cun'es that mak.e up the two-phase envelope do not ror-
respond to the heat capacity at ronstant pressure. We may speak. of the heat capacity at sat·
uration. cv...
or cI-". related to the heat capacity at constant pressure by the equation:

cv.":r:I'+("")
·r
dP"
(JP T dT
(2.19)

or. (2.20)

Since the term dh"rdP is negative. the curve for the enthalpy of the saturated vapor
passes through a ma~imum. Because of the very low value of the term dhLfdP. the curve
for the saturated liquid is practically merged with the isobars.
At a pressure greater than the critical pressure (curve A'D' in Fig. 2.2), no change in
phase will be observed. and the variation of enthalpy will be evaluated solely as a funClion
'6

of the heal capacity of the fluid at conSlant pressure. However. it will be noted that this
heal capacity rna:c.imi7....-s al approximately the critical temperllture. being more pro-
nounced as the pressure approaches the critical pressure. If the pressure is equal to Ihe
critical pressure. the critical isobar has an inflection point with a langenl parallel 10 lhe
enthalpy a:;is and the heat capacity al constant pressure lakes on an infinite value.
H

In the "vapor domain. the isobal"; pertaining to low pressures arc practically merged wilh
the curve (independent of the pressure) that can be drawn for a perfeC1 gas. For a given tem-
perature. lhe diagram thus prescDled "ill bring oUllhe deviations from the perfect gas laws.
with regard 10 the enthalpy. We find Lhal these are negative: the enthalpy or the '"' ftuklls
~ than thaI of lhe perl'ed p!I. especially since the pressure is higher for the vapor state.
This phenomenon reverses itself however when the lemperature is very high as compared to
the crilkat lempcralUrc. This deviation for the liquid stale is very substanliaJ (in absolute
value) and is made up or IWO terms: the deviation with respect to the saturaled vapor. whose
magnitude depends on the vapor pressure. and the heal of vaporization (sign reversed).

2.3.2 Heat of Vaporization

As we have mentioned repc8ledty. the heMl or VlIporiZlllion dene1lSC5 when lemperJIIlure


In(:rell.'iCS.. .nd Qncds 11se'1f out "I the eriUa,1 ltmperJIIlure, when the liquid and vapor
phas.::$ arc the same. Figure 2.9 shows some examples of this changc.

,
f
,30
j

i"
>
• --
110
ol-----'r---,-'----'--,--'---'-,-'---'--'-'r-'-'
'00 300 "'"
Temperalure (K) "'"
tiJ:urc 1.9 Variation or heat of vaporization with Icmperature:
IhI: " ....lbr>Cs C , - CHI" carbon dioxide and mclhal\Ql.
47

Experimental measurements of heal of vaporization are relatively rare. and most ollen
its value is derived from vapor p.($Sure measurements by applying the Oapeyron equa-
tion. Its value is cMcntial for a precise calculation of the enlhalpic properties in the liquid
phase. It is appropriate !O recall here the TroufOn equation according to which. 81 atmos-
pheric pre$Sure, the entropy of vapori1..;llion, as related to the heal of vaporiution III thai
temperature. is equal to 21 cal, mot-I. K- l This equation provides a very useful. btll rather
rough approximation. as shown in Table 2.7.lhal gives the values of the adimensional quo-
tient 4h"fRT at boiling temper-Hure al atmospheric pressure-It must be remembered thaI
the Ttouton equation is nOI applied to Iluloassociatcd romponel1ts.
Equation (2.14) may be wrinen as:

tJr" = _ R d In (I"') /lZ" (2.21)


1
d
r
A pr~se application of the vapor pressure values with the goal of calculating the heat
of vaporization by application of Equation 2.21 requires a corn:lation of these values with
the aid of one of the previously described empirical equations, ll!l well 3.5 data for the com-
pressibility factor (or the molar volume) of the vapor phase (equation of state for exam-
ple) and of the liquid phase. For example. at moderate pressure we can apply the equation
of the virial state (sec Chapter 3. Section 3.2.2.I,and Chapter 4, Section 4.1) to the vapor
phase. and calculate the molar volume in liquid phase using the Rackcu equation
(Chapter 3. Section 3.2.1.2).
Variation in the heat of vaporization with temperature can be evaluated using the
empirical equation proposed by Watson:

"""
",
-- (2.22)

"""" 1--
r,
r,
The precision of this equation has been improved by Thek and Slid [1966. 19671 by
adapting the value of the exponent to the nature of the component.

Table 2.7
Entropy of adimensionaJ vaporiUllion. !:J,"IRT.
al almo6pheric pr=UIl'

Compound !:J,"'RT Compoun<.l !:J,"IRT


Melbane
Ethane
8."
9.57
Cydohuane.
Benzene
",
",
Propane
,,·Bulane
9.78
9."
Totuene
Melhanol
",
",
bobutane
/I_Pen lane
9." Ethanol
Acetol\C
IU
10.1 10.9
/I_Hexane 10.2 Acetonitrile 103
/I.Heplane 10.3 Waler 13.2
/I·Octane 10'
o EXAMPLE 2.2
Calculation of the heat of vaporization
for benzene using the cI.lpeyron equation
Around the boiling tcmJ'{'ralUre at atmospheric pressure. the vapor pressure of ben-
lene may be calculated by applying the Antoine equation:
b
logm"" =
c<.
/I - - - (2.15)

The numerical values of the parameters are listed in Table 2.5: /I = 6.01905
b = 12~.637 c = 22Q.069. with the units "e. kPa.and the base 10 logariltlms.
Additionally we will usc the following data:
• molar volume in liquid phase: vi· = 95.60 cml/mol
• second virial coefficient at 8O"C; 8 = --943 cm)/mol.
In order to be able to apply the Clapo::yron equation more easily. we shall convert the
Antoine equation to 51 units and use natural (Neperian) logarithms (In x = 2.30258
loglO:r) so that EqUalion 2.15 becomes:

I ""(P) , b' =20.76713- 2773.779


n a=lJ-c'+T(K) T(K)-53.081

The pressure is equal to atlilospheric pressure: p~ = 101325 Pa. and the temperature
is derived by applicatiOfl of the Antoine equation in the form:
b'
T= -c'
u'-In P

Wc find: T = 353.24 K.
The Oapcyron equation is writtcn as:
dper Mrs
-d-T = T(vV.rs_ II L") (2.8)

and thus:

We will e:t"press the derivative dPsldT from the Antoine equation:

_'P"_ = b'P" = 3 120 PaJK


dT (c' + T)2

It is also necessary to calculate the molar volume of the saturated vapor.

"ltD= RT +8= 8.314·353.24 _943.IO-6=2804I.10-6mJmol-1


per 101325
49

We end up with:

!JJr" '" T(v I:" - v t ..) c::;'" 353.24(28041 - 95.6).10- 6 .3120.=0 30794 J. mol-I

This result is "ery close to the clCperimenlal value (30.760 J . mol-I). If we had com·
pared the vapor phase 10 an ideal gas and neglected the molar volume of the liquid.
we would have arrived at 31.938 J . mol-I with an error in Q.cess of 3.7%.

2.4 CALCULATION OF THERMODYNAMIC PROPERTIES

The method most generalJ)' applied for determining the thermodynamic properties of a
system consists in separating the contribution corresponding to the translational, rOla-
tional. and vibrational energies of all or part orlhe molecule and the roalribultoD ~ltinK
frolllihe mol«ablr IntC:rllction rora:s; tbe devllltiodll fl'(Hll the ide.. IPS"1ft, 01' the Mresid_
u.1 p~rtksM, oornspond 10 11Ib; 5eCQnd contribution. These proper1ies cannot be
considered corrective terms. We may not disregard them. except at low pressure or more
exaclly. at low density. since a condensed liquid or solid phase may be stable at low pres-
sure.
To evaluate these residual properties. the real fluid and the ideal gas may be considered
either under the SlIme conditions of temperature and pressure. or under the SlIme condi-
tions of temperature and volume. For enthalpy. for example:

h~(T.P) = h(T.P) - h '(T.l') (2.23)


h,..(T.v) = h(T.I!) - h '(T.v) (2.24)

Note that if the temperature and the pressure are the SlIme for the real fluid and the
ideal gas. the molar volume is not the same. and if the temperature and the molar volume
are the same. the pressure is different.
The residual properties at a given temperature and pressure. on the one hand. and at a
given temperature and volume. on the other hand. arc not identical in all eases.. as we shall
see. Thermodynamic statistiC!; fin>t yield the residual propenies at the given temperature
and volume. and it is the same for most equations of state. Yet the conditions imposed are
most often temperature and pressure and we refer most often to the residual propenies at
II given temperature and pressure. which we will do from now on exccpt for specifIC situa·
tions.
To calculate them we generally call upon the relationships that e:tist between the varia·
lions of Ihe thermodynamic propenies at constant temperature. dUro dH r • etc.. and
depending on the case. the variations in volume dV. or pressure dP. If the behavior of the
system is represented by an equation of state. and if this equation is explicit in volume or
pressure. we arrive at the residual propenies at the given temperature and pressure. or i1t
the given temperature and volume respeclively.lt is therefore imponant to specify the dif·
ferences between these two types of residual propenies and the equations that link them.
We shall do this by calculating residual enthalpy and Gibbs energy.
50

Generally. X stands for any thermodynamic properl)' (internal energy. cnthalpy.


entropy. cle.). The calculation of the residual value from the given "pressure, volume. tem-
pc'Tluurc" is based on:

X (T,P)z J:[(~~)T-(d~'),]dP (2.25)

and: X (T,V) = J: [(:~)T -( aa~')J dV (2.26)

2.4.1 Residual Enlhalpy

The dcrivati\'c for molar enthalpy as it relates to pressure at constant temperature is


expressed by the equation:

(iJp"') =,,_r(a,,)
T ilT f'
(1.51)

shown in Chapler I. Section 1.6.1.


For the ideal gas. the "unation of enthalpy with pressure ;s zero (Chapler 1. Eq. 1.68):
and we have:

Ir...(T,P) = 1:[ r( :; )J
11- dP (2.21)

Applying this equation supposes Ihal we may express the volume as a funclion of pres-
sure. lhat is. using a volume explicit equation of state. This is not always the case. If lhe
equation of state is simultaneously applied to booth lhe liquid and vapor phase, it will for
certain values of pressure yield at leasl two molar volume values. One value is valid for the
liquid phase and lhe other for lhe vapor phase. The equation has to be prC$Sure explicit. Of
coun;c. the preceding integml;on may be perfonned by parts. It should be remembered
that isothemlal variations in enthalpy are expressed. preferably from pressure variations:
variations in internal energy are expressed as a function of volume variations. So we will
first calculate the residual term lhal relales to internal energy at a given lempemture and
volume. To explain lhis calculation in funher demit we shall specify the values for temper·
ature. volume. and pressure.llte derivative for internal energy as it relales to volume al
constanl lemperalure is l'xpresscd by the equation:

~,) .r("')-p
( (lvr (1.50)
(lTv

II is zero for ideal gas (Chapter 1. Section 1.7.1. Eq. 1.67). and the residual term at the
given lemperalure and volume are calculated using:

(2.28)
51

To obtain the residual internal energy at Ihe given temperature and pressure. we wrile:

1I(T.P,II) -11'(T.P'II' '" R:)


'" [u (T.P.v) -11'(7;1" '" ~~.II)] .. [11'( 7:/" '" RIJT,v) _11'(T.P'v" = R:)]
However, wilh regard to the internal energy of ideal gas-the difference:

( RT)(
,,' 7:1" .. -;;-,11 -II' T,P.II"= RT)
P

is lero. We therefore obtain:

To arrive alttle residual leTm for enthalpy, it suffices 10 remember the equations:
h=u+/'II and "':lI'+RT Ihatis(h-h')=(lI_u')+PI1_RT
We then obtain the equation:

h(T.P) -h'(T.p) + r [r( ~~ L- p] d" .. Pv- RT (2.29)

2.4.2 Residual Gibbs Energy

We shall use the same process to derive the equation for residual Gibbs energy. but we
shall nole important differences.
The derivative fur Gibbs energy wilh respect to prt-ssure at constant temperature is
equal 10 the volume:
(IA5)

For ideal gas.. il is nOi zero:


(1.71)

We therefore write:

(2.30)

I( we cannot calculate lhe volume as a function of pressure (pressure explicit equation


or Slate). lhen liS done previously. we will fin>t calcul;.le lhe residuallerm atlhe gi\'en lem-
peralure and yoluml" lhat relates 10 Helmholtz cnergy. To cxplain this calculalion in fur-
ther detail. we shall specify lhe \'alues for temperature. yolume. and pressure. The deriya-
11.

'- -~-

,P'

nTUloh

J[ J
lh~ ,[-
.
'
. I

:=-

-~

o
,~." 1
I.' -
53

Table 2Jl
Expression of residual values

,,_(T,v) .. u(T.P.v)- ".( T,p' .. R"T ,")" [ [r( ~~)" _p] d.. (2.23)

h...( T, P) " Ir{ T.P.v) -Ir'( T. P, v· )" r[" -r( :;. ),]
,=,~: dP (2.27)

Irrn(T.f')" h(T.r.,,) - h'( T.P. v' . R;) ..[' [r( ;; L-pJ dv + PoJ - NT (2.29)

S,..{T,P)"gCT.P,v)-g o( T.P,v o • pRT) .. J.'~ (NT) p,


-f'+-;; dv_RTln RT + Pu - RT (2.321

2.4.3 Fugacity

The potential that determines the equilibrium of a pure substance between diffcrcnl
phases is the molar Gibbs energy as shown in Equation (2.j).ln mixtures. it is the chemical
potential. meaning the contribution of each component 10 the Gibbs energy of the mill'
lure. From a purely formal point of view, resorting to these properties has cerlain disad-
vantages: molar Gibbs energy cannol be calcuhllcd in relation to an arbitrary origin. and
tends toward __ if the pressure nears zefO. Furthermore. it is regrcnable that between
pressure and Gibbs energy there exists no equation that is as simple as the one previously
derived for ideal gas:
dg;=RTdlnP (1.71)

Lewis [1923J proposed representing Gibbs energy using an auxiliary property. fugacity
(initially referred to as "escaping lendency"). whose isothermal variables are defined by
the equation:
dgr= RTd Inf (2.35)
"
As we ClIll see. for Gibbs eucre', ruglldt)' phl)'s the urnI' role for II real fluid IIlI p~ure
pial's for ideal 811s. This analogy is completed by defining the limiting condition:
Ip ..... l i(/' ..... O (2.36)

Fugacity presents itself as an effective pressure,lhal is 10 say.lhe value Ilial mllst be sub-
stituted for pressure in order 10 presen'c the expressions for ideal gas. always with respect
10 calculation of the variations in the Gibbs energy. For residual Gibbs energy. we can sub-
stitute the rugadly coefficient;
I
1jJ= - (2.37)
p

and wrile: g(T,P)-g'(T,P):; RTln ~:; RTln 41 (2.38)

So. by applying the Equations (2.30) or (2.32):

RTln (jl= fa!' (II - R;) dP (2.39)

PTJ dl'-RTln-+Pv-RT
O(-1'+- P,
RTlnljJ=
f • v RT
(2.40)

For II pure substance al low pressure. fugacity is numerically dO!\C to the pressure for
the gas phase and the vapor pressure for the liquid phase. as we shall see.

2.4.4 Calculation of Thermodynamic Properties in the liquid Phase

We have emphasized the continuity that exists between the liquid and vapor pha.'ie1i. and the
ambiguity of these terms. The fact remains that the distinction between these states is often
imponant.lf we apply the equations Ihat allow for the cakulaliOll of residual values for a flUre
substance under conditions ,,'here it is characterized as a '·Iiquid·', these equations then incor-
porate the variations of the thermodynamic functions accompanying the change of phase.
Figure 2.10 lists five states in the diagram (temperature versus pressure). For points 1.2.3.
and 4. the temperature is less than the eriticaltempcrnturc. Point I designatcs a condensable
vapor and the pressure is less than the vapor pressure. Points 2 and 3 are merged at coordi-
nates T.P where the pressure is equal to the vapor pl\.'SSure. The first of these points (point 2)
represents a saturated vapor: the 5eCOfId point. a S<1turated liquid. The)' are situated "on either
side·' of the vapor pressure cuTVe.Point4 represents a liquid phase that is obtained. for exam·
pIc. by compression of the saturated liquid. Finally point 5. located at a temperature higher
than the critical temperature represents a nuid state that we may call "supercriticar',
Calculation of the residual enthalpy or Gibbs energy temls that relate to states 1.2. and 5 by
application of Equations (2.27 to 2.34) does not ]Xl6C any problem. 'The integration path
encounters no change in phase. On the other hand, for the saturated liquid (point 3),or under
pressure (point 4), we arc led to perfoml the integration within the range of phase change.
This forces us to suppose that the expression (equation of state) that we are using provides
the deriv3lives for the thermodynamic function in question as it relates to volume (cxpres-
55

,,---------,

T' T'
I
I
.
't I
I
i' ,I 2

2 +---,----'---,---'----1
"'"
Temp8f8lure (K)

}1f:ure 2.10 Colrulati<!n of IhermOOynamic properties "". function of


temperature and pteMurc:.

sion 2.26) or pressure (expressiOll 2.25): values (without physical reality) whose integral cor·
rtttly describes the variation of the function during oondensatioo. Such is the implicit postu-
late 10 which we shall return with regard to the equations of state. We ClID also bl't'llk dO~"1I
the cak:ulation of II themaoo)nJImH: fWldion into !inera! steps "bile JlltiU"iDJI: tbe ph)'Sial
IlIId the predslon. We shall specify these steps ror enthalpy. Gibbs energy. and fugacity.

Calculation of Enthdlpy

We can firsl c~aluate the residual enthalpy term relative to the saturated vapor (point 2)
by application of Equation 2.27 (or 2.29). and derive the enthalpy of Ihis vapor:
111,'(7:/4 = Ir'( TJ4 + h~(T.P") (2.41)
In order to move to the saturated liquid (point 4), we subtracllhe heal of vaporization:
(2.42)
56

and finally. for the pressurized liquid (point 4). we include the variation of the enthalpy of
lhe liquid with pressure(Eq.1.51):

!r ( T.P) '" 1I·(T.fX') -+- hl:e,(T.P"') -


'
,~h" + f: (,,1. _ (a;;),.)
T dP (2.43)

This last term is generally low compared to the preceding terms, in particular compared
10 the heal of vaporization.

Calculation of Gibbs energy and Fugacity

As wilh enthalpy, we first calculate Ihe Gibbs energy or the fugadly of the saturated vapor.
8\'( T. P") '" g'( T. P") + K,,,, ( T. P") (2.44)
or. by expressing residual Gibbs energy using lhe fugacity CQCfficienl;
gY(7: P"} '" S'( T./"') + NT In Ip" (2.45)
and thus. by applying Equation (2.39):

RTlnrp"=
f ~( v- RT) dP
\I
p (2.46)

Observing Ihal the equilibrium condition imposes equality of molar Gibbs energy Ol'"
fugacity in the vapor and liquid phase. we have:
(2.47)

(2.48)

Finally. for a pr~uri~ed liquid phase (point 4). we will include the varialion of Gibbs
energy or fugacity with pressure:

RTln(fL~P»)= J: lJLdP

or. fL(7:P)=f"exp
U' ",.)
~
-
RT
d/' (2.49)

The lJL/RT ralio is generally low since it is equal 10 the ratio of the OIolar voluOic of the
compound in queslion to lhc molar volume of ideal gas at atmospherk pressure. The
fugacity of a dense phase therdore varies with pressure and lhe term:

'1' '" exp (f ' ",.)


RT dP
f'" (250)

called lhe Poynting correction. is dose to unity at moderate pr~ure. To calculate it. we
oftell acknowledge that the liquid phase is not compressible. and we can write:
",(p_1m)
'1'= exp ( RT I (2.51)
57

o EXAMPLE 2.3
Calculation of the fugacity ofethane at 25"C
Using lhe data presented in Table 2.9 (fint and second columns). we will calculate Ihe
fugacity CQefficienl of ethane as a function of pressure a\ 25"C.
Figure 2.\1 shows the variation oflhe difference 11- RTIP (Table 2.9. third column) as
a function of pressure, and permits the graphical integration necessary for lhe calcu-
lation of fugacity in the vapor phase (Eq. 2.39). The results of this integration are
shown in Table 2.9 for several values of pressure. They are used to calculate the fugac-
ity coefficient and fugacity. This value follows the pressure; the difference is greater as
Ihe pressure rises.

...
,
~ "'"
"!
~ ""
•,
>
'00

0
0 , 3 • ,
P,l,tSSUrfI (MPa)

liKure 2.1.1 Calculation of th" fugacity ooefficiem for ethane al 2S"C.

Table 2..,
Calculation of th" fugltcity of ethane in v.. pot phase al 25"C

,. "
,,- NTiP
f}-';l" • f
(MP.. ) (~n\l'n\ol-Il (MP"·cn,l·mol- l ) (b.u)

OJ
,,.,
0.'
24602
4767 -'"'
-190.6
-18.6
-9·U
0.'"
0.963
0.'"
".111
-196.8 -191 0.926 9.26

2
".,
2'"

,"'"
-203.5
_211.4
-291
-395
0.880
0.853
13.3
17.1

"
3
no
,,,., -221.5
-23-l -""
"'''
0.816
0.180
20.'
2).4
35
•4.1876
456.5
))7.4
_251.7
-282.) ......
_1)7 0.14)
0,," ""'.,
".2
"'.85 -"" -'" 0.689
56

Extending experimental data to saturated vapor (p .. 41.876 bar), we obtain fugacity


al saturation, 28.9 bar. relative to 00111 vapor and liquid in equilibrium. If we wish to
calculate the fugacity at a higher pressure. we apply Equation 2.51 that requires lbe
knowledge of molar volume of the saturated liquid. Using 111..<7 = 9S em l . mol-I and
assuming thallhe liquid is not compressible. we obtain. for example (Table 2.10);

T.blel-IO
Poynting corr~-ct;on applied 10 elhane
bcl ...~en SO and 100 bar. at 25"C

I'
(bar)
• f
(bar)
SO 1.031 29.16
75 l.lJS 32.75
100 125 J6

2.4.5 General Equations

To evaluate a thcOl1odynamic property such as enthalpy or entropy, we are led to proceed


according to the following steps:
• Choose an origin for which the values (arbitrary) will be given as standard enthalpy
or enlropy (ideal gas. pressure po '" 0.1 MPa): i.e. at To.p o we have h O (To.PO).
SO (To'PO)
• Calculate the values of enthalpy and ~ntropy. always at standard state. but at temper-
ature T: T.po.l. o (T.PO), SO (T,PO)
• Cakulate the values for enthalpy and enlropy in the ideal gas state at temperature T
and at pressure P: T.P, h' (T.P), s· (T.P)
• Finally add the residual property (h - h')r,p, or (s -s·h;,.
thus slOting for enthalpy:

h '" ItO(To.f"') + [hO(T.P") -hO(To.P")J + [h·(T.P) _hO(T,P")J + (h - h'hr (2.52)

and (or entropy:

(2.53)

The ealculations used for the ide~ll gas may be eltprcssed (bearing in mind the (aetthat
the enthalpy of the ideal gas is independent of pressure) as:

h",hO(To'P")+ f: cpdT+(h-h'hr (2.54)

T cOP
5=sO(To.P")+
I ToT
...!-dT-Rln-+(s-s'hr
po .
(2.55)
59

CONCLUSION

We have jusl seen that .he calculation of Ihcrmod)'namic properties i! based on Ihe under-
standing of (he equations relating pressure, volume. and temperature, illuSlraling the
importance of the development of the equations of state. We have also emphasized the
particular role played by certain properties such as the critical points, vapor pressure, and
heal of vapori7.ation. They make up OUT minimum database.
We must. of course. go beyond this minimum dalabase. It is rare to have 81 our disposal
for a compound a complete set of values for molar \'olume, enthalpy, heal capacity.
entropy. c1c.. for the enlirc range of pressure and temperature. We must therefore apply
mClhods thai are as predictive as possible. The following chapters are devoted to Ihis sub-
jeci.

REFERENCES

Ambrose D (I'118a) l1lc correlation and C!itimMion of vapour pressures. I. A compari:lOll of lhrl-e
vapour pressurcc C<Jualions. J. Ch~m. Thunrod,.,u,mia., 10.165·169.
Ambrose: 0 (1911\b)The ron-e1alion and estimation of"apour presIIures.II.A new proa:dure foresti·
malion and eKlrapolalion.J. Ch~m. ThumodYmlmil".J, 10.165-169.
Ambrose D (l980)The oom:lallon and eSlimation of vapour prcssures.lll. Referccnce values for 10'"
I""ssurc "timalions. J. Ch~m. Tlterm{){/p,ami<:-s, 12.811-819.
Ambrose 0 (1985)The Evaluation of Vapour Pres.ure Dala. !'r;vale communication.
Buublik T. Fried V. Hala E (1984) The Vap(mr Pressures of Pure Su/mancu. Elsevier.Amslerdam,
Carrulh OF. Kohayasbi R (1m) Ind. Eng. CMm. Fundam.. II. S09.
Dymond JH. Smilh ED (1980) Thr Vinal CoeffirimlS of PI".. Gases and Mix/ura. Oarendon !'ress,
Oxford.
Daubert R. Danner (1986) DIPPR Data C"mpilalim,. AIChE J.• Ncw York.
Ha,lacher EA. Braun WG (1970) A foor parameter eKten,ion of the lheorem of corresponding Sla-
tes. h,d. Eng. Ch"",. Frocus Dr$, D.>·./up.. 9. 419-483.
King MB. AI-Nanar H (1974) A mctltod for correlaling and eKtc!>ding vapour prcssure data to lo..'cr
lempcralun:5 u5inllthermal data: vapour pn:sl!ure C<Juations ror lOme: n_alta""", below lhe normal
boiling point. Ch..m. Eng. Sci.. 29. 1003-1011.
Lewis ON. Randall M (1923) TI'umod,.,ra"'ia 'JIId ,h. Frte En.rgy of Ch.micol Subslam"'s.
McGraw-Hili Book Co.. first edition.
MOSSI:lman C. van Vugl WIt. V"s H (1982) J. 0,..", £"g, Onla.21.246,
Reid RC. Prausnill'. JM. Sherwood Th K (1916) l'h Pro~nj.s of Gasa and Liquids. tbird nlition.
McGT'lIw·Hili Book Co.
Rcid RC, Prausnin JM. Puling BE (1987) TI" P,,,p,,,,ia "f GlUes ami Liquids. founb edition.
McGraw.Hill Book Co.
Stoll SW. Osbom AG (1979) Representation of vapor pressure dala.J. Phys. Chcm..83.2114-212J.
TejaAS.Oude M. Rosentbal OJ (1989) Novel methods for lhe measurement of lhe crilical properties
of Ibennall~ uRSlable nuids.. Fluid Phase Equilihria.52. 19J·200.
60

Thek RE. Sliel Ll (1966) A nc'" reduced vapor pressure c'l""cion. A IChE I.. 12.599.
Thet RE.Srici LI (1%7) {Erralum 10 pr~-ccding reference).AJCh£ 1.• 13.mb.
Rogalski M. Malo Chain FA. Carrier B (1991) Vapour pressures of hydrocarbons. """ldis81;on,
eJl1rapoialion and prcdi<:tion. eh"",. Eng. Sci.
Ruzicka K. Majer V (1994) SimuhaMous lrcalmenl of vapor pr~urc~ and rdated thermal dala
between tile triple and oonnal boiling lempcrntures for ,,·alkanes c,.c,...J.
P!lrs. Ch~m. Ret Dala,
23.1-39.
YaWll CL, Yang HC (1989) 10 estimate vapor pressure easily./I}"droca,lJon PrrKQsillg.68.( 1O).65-fl8.
I
3 Predicting Thermodynamic
Properties of Pure Substances
General Principles
Corresponding States
Group Contributions

In reviewing the behavior of fluids. we have emphasil.ed thai knowing certain properties
such as lhe critical points lind vapor pressure. for example, are indispensable 10 Ihe calcu-
latioll of lhermodynamic quantities. We have also specified the steps that this calculation
would most oflen follow: calculation of the properties in the ideal gas Slate, lhen the resid-
ual values. These steps aTt based on the equations that linlr:: pressure. volume, and temper-
ature. It must be stressed lhal wilh few exceptions.. these equatiolU have not been deter-
mined for mOSI pure substances. and Q !oniori. for mixtures. We must therdore use predic-
tive methods. With limited initiallr::nowledge.these methods provide aocc$S 10 all thermo-
dynamic properties. These methods exist, and their limitations cause them to change. The
simplicity and efficiency of some methods lead to misuse. We are in difficult territory
where any conclusion is obsolete from the moment it is drawn.
In essence. the problem facing us is one of accounling for the consequences of molecu-
lar interaction forces at the macroscopic level. Limiting ourselves to Mnon_electrol)'h:"
solutions, it is therefore appropriate to review II number of simple com:epl5.
Essentially, the forces of intermolecular attraction fall into four categories
(Emschwiller,1951,p.I363-1367J.
• Orienl.lton rol'«'li are present between n'ollX'ules having a permanerll dipole
moment, This dipole momenl reflects the asymmetry of electrical charges due to the pres-
ence of electronegative atoms,
The interaction energy depends of rourse on the respective orientations of the dipoles
bUI, according 10 the Bolt7.mann slatistics. II,waging may lake into account all orienta-
tions. Using Pj for the dipole moment.' for the distance between dipoles. and II. as the
Bohvnann constant. we find that:

(3.1)
62

• Indudiun fort:e5: a permanent dipole may induCt: an electrical asymmetry in a neigh·


boring molecule lhal is nOI polar. but polarizable. Interaction energy between a permanent
dipole and an induced dipole is established. which depends on Ihe polarizabilily a of the
molecule wilh the induced dipole. [ts is expressed as:

(3.2)

• Dispersion forces; we must take inlO account lhe cohesion forces thal exist between
non-polar molecules such as lIydrocarbons. We may imagine lhal spontaneous dipoles
exist that are of 110 consequence in time or space. but Ihal are themselves susceptible to
interaction by induction. A simplified calculation yields the following expression for the
energy of dispersion as a function of polariUlbility Cl. the O$Cil1ation frequencies v. llnd
Planck'sconstanlli:

(33)

• U)'drogen bonding: finally, we know that two molc<:ules may be boulld by a hydrogen
"bond". Such is the case with alcohols undergoillg polymer chain autoassociation and, of
COUTSC. with waler. These bonds may form between molecules of a similar nature (aut035-
sociation) or molecules of a dissimilar nature (complexalion) as with water/alcohol solu-
tions or ether/alcohol solutions.

BcsidL'S the intermolecular attraction forces. there are repulsion forces as may be
observed by the low compressibility of the liquid phase. These forces prcvent molecules
from approaching one another beyond a eenain limit. such as "hard spheres (or chains)".

It is very difficult to tcll what boils down to the forces of orientation. induction. and
dispersion in a macroscopic property even though it represents molecular interactions
such as heat of vaporization. We need to remember thlll if we are talking about complex
molttules. molecular interaction is the result of inlcrlldions al "'ork among lbe
component gruuP'! of two neighboring molecules. For example. Figure 3.1 shows the
variation of cohesion energy E, (itself derived from the heat of vapori7.ation) for linear
paraffins and some nitriles as a function of the number of carbon atoms ]Mc)'er, 1971], For
long chain hydrocarbon nitriles. the dipolar interactions arc somewhat "diluted" as Ihe
length of the chain increases suclltllllt the amoum of orientation energy. Ell' der.-reases. The
shift of this asymptote compared to straight line EJIl} which refers to lhe paraffins
represents induction energy. We note that the dispersion forces. EtJ , which are solely
responsible for the hydrocarbon cohesion forces. also make up the main cohesion forces of
the nitriles.

!\I()!;l predictin methods lhal ,,'e Shlill enCGunler "cre de.·clopi:d for non-polar mole-
cules, in particular the hydrocarbons. It is possible thaI when applied to polar compounds
they lead to good results. but prudence dictatcs that "'e lreal such rcsullS liS fortunllte coin-
cidences and refrain from an application thai would most often yield gross errors.
Ncvertheless.. we shall point out somc widely applied extensions.

p'
63

/
,
lEI
./
~
/
,
,'E .
/
6 10 14
,,
18 ~ ~

Number 0/ carbon atoms

HI""' 3.1 Comparison of the rohcsion energy ofparaffins and


nitriles IMeyer cf ../.• 19711.

3.1 TECHNIQUES OF MOLECULAR SIMULATION

It is not within the scope of this study to introduce molecular simulation techniques. They
IIrc in and of themselves II true specially. We shall menlion them only briefly in order 10
emphllSize their potential and rapid development.
Our knowledge of molecular interactions and the progress shown in the field of scien-
tific calculators allow us to calculate the mllCfOSCQpic properlies (or II number of mole-
cules. A molecular model and a representation of the energy of intermolecular interaction
all: necessary. We apply either the MOnlc-Carlo method or molecular dynamics.
The Monte-Carlo method randomly produces several molecular grouping<; and rClaim
only those that obey the Boltwtann statistics for a given volume and temperature. Molecular
dynamics uses newtonian mechanics and solves Ihe equations for molecular movement. In
both cases, the macroscopic properties are estimated by obtaining appropriate a'"eragcs.
A fundamental question is posed when ....e apply these molecular simulalion techniques.
What is the validily of the applied potential? In many cases. we have an empirical model.
such as those of Lennard Jones or Kihara (see Eqs. 3.4 and 3.8). We may also consider that
the intermolecular interaction forces resull from inleractions between the groups that
make up Ihe complex molecules. It is therefore advisable 10 remain suspicious of the
resulls of these calculations and compare them to experimental values.
Furthermore. they generally require very complicated calculation methods. For Ihis rea-
son. they may not be COnsidered operatiOnal subslilutes for the empirical models applied
by chemical engineers. On the other hand. molecular simulation is a rapidly evolving disci-
pline [Gubbins. 1989]. In the future. it will undoubtedly produce reliable values and sup-
plant experimental data to a certain extent.

3.2 THE CORRESPONDING STATES PRINCIPLE

We have repeatedly mentioned intermolecular cohesion pootentials. MallY expressions pro-


posed for them are. as we shall see. used for the calculations for molecular simulation.
Figure 3.2 provides two classic e:tamplcs of such expressions. The first is the Lennard Jones
pootential. resulting from a c-ombination of attraction forces acting lIt an IIverage distance.
and the repulsion forces that predominate at short distances. Its expression:

(3.4)

sho,,""S two intrinsic parameter.! of the compoound in question: the valUl: for the distance
between the centers of attraction at which the potential cancels itself out. 'a. and the mini·
mal value of potential to. The second example is the "square well" example. The molecules
arc treated lIS "rigid spheres" and the dislance between the ccnters of the molecules always
remairu; greater than at a rert<lin value. In an imerval defining the "width" of the well. the
potential takes all a constant value and beyond it cancels itself out. This very schematic
model allows for relatively simple calculations alld itself introduces the two characteristic
parameters: the width and depth of the well.
In general. if we state thaI:
• the poh:ntials related 10 the degrees ofinterual freedom of molecule'S (lranslatiOfl. rota-
tion. viW,Ition). and to external freedom (cohesion) may be expressed independently;

,-,---~~------.

I
11'
I
I I
L ,-I
,-,-,--,---1
-, '-r-,--,-
o , , ,
~l~re:U Lennard Jones polentialllnd -Square Well" potential.

1
65

• the cohesion energy of a system is expressed L1sing the sum of the binary illlemclions
between the centers of 8tlraetion:
• these interactions are reduced to the dispersion force!! and may be calculated using an
upression in the form £., £11 F (,lr°), in which the fUlletion Fis a universal function.
since only ell and ,11 are related 10 the nature of the substance. It is well understood
that Ihis function F may differ from that of Lennard Jones.
It is then possible 10 demonstrate Ihal the macroscopic cffccl'l or
molecular interactions
arc expressed as a funetion of (I) two paramclcr5 characteristic only of the substance
(characteristics corresponding to If' and ,0), and (2) variables of slate such as pressure 81ld
temperature. The corresponding stales principle is therefore nOI an axiom, but a demon-
strable theorem.
However, it is appropriate to point out thaI this law was stated by van der Waals well
bo::fore studies of intennoleculllr potentials.
The equalion of stale that is derived from ·'the configuration integral" by applying Ihe
pre<:eding hypotheses has the following fonn:

z--:r(' ,)
(T' ?l.aJ

where Z is the compressibility faclor, (is Ihe Boltzmann constan\. and ~ is Avogadro's
number. Stating that it verifies the critical conditions (Chapter 2, Eq. 2.4). we obtain the
values for Z" e/Ii.T,. and "/?l.aJ. which arc universal. meaning thatlhey are the same for
all substances satisfying the initial hypotheses.
In particular. we rna)' define a characteristic temperature"'" = £Iii.. and a charncteristic
volume ,,- = 'f.cr, or any olher group of macroscopic parameters. The choice is generally
taken from the critical points themsel,'es. preferably the critical temperature and the crili,
cal pressure due to the imprecision distorting the critical volume values.
We define the reduced variables:
reduced temperature: T, = TIT,
(3.5)
reduced pressure: P, = PIP,
and lhe corresponding stales principle may be stated in a very simple form:
DC1'lallol1li from the idcal Ill'i la\\"lI (or l'C'liidual "aIUft) depend onl)' on redu(fil
1'lIrillbl~

Figllre 3.3 shoW$ thaI the change in compressibility faC'lor Z is aC'lually a function of
redllct:d pressure P, at the given reduced temperature (here. 0,96. \.02. and 1.2) regardless
of the nature of Ihe compound in qucstion (here, methane. ethane, propane. and n·blllane.
represenled respectively by the symbols 6, •. 0 and e).
If we inctude this principle in the calculation of the compressibility factor. it is then also
applied to lhe delermination of the fugacity coefficient, the adimensional residual terms
for enthalpy (h - h')lRT. entropy (.1"- ,,')JR, and heat capacity (cp-4)1R. We shall demon-
strate its use for the residual enthalpy and for the fugacity coefficient.
To calculate the residllal enthalpy we apply Equatioo 2.27:

(2.27)
,- 0
0 0
0

•• ,
0

,"• • •-

0
0
0


0
0

• 0
.•
is
0

0
• !.,
0
• • 0
~
~
0 0
0

• a- •
0
0
0 0
0
•~•
0



0
0
.:
0


,

0 0
•• • [
0


0
0 0

0
0
0

0
~ -
I ,

~


<
••
0

0
0

0
0
0
• • • .:
• 0
0
J
s -,
~

• ••
0 0

..0
0 o
0
0
0
i
• ..•• •
,
~

• ..
..
0
0
0
••
00
]

0
~

~
--
0 00

• "
0


••

0-
••
0 "
,•
0
H
~"!
••
..•=
o.
H
o
• o

67

We c:tprcss the volume by the equation:


RT
v:z-
"
and so:

Thus we oblain:

"_(ToP)
RY
.-f'ol'iJT T, (02) dP
T(az) r dP.-f"op,ar,,.' (3.6)

Similarly. 10 calculate the fugacity coefficient we write;

tnlp:
f'(' I ) dP>&
---
oRT!' 0
dPP,
fe, (Z-I)-' (3.7)

II can be seen Ihat if the compressibility factor obeys the corresponding slales principle:.
Ihat is 10 say. it is a function only of T. and of P, then it is the SlIme for adimcnsional resid-
ual enthalpy and lhe fugacity coefficient.
Yel, this corresponding stales principle provides only a first approximation. sometimes
a rough one. of rcsiduallerms. The deviations are more particularly marked when "'C apply
it around the critical point or in Ihe liquid phase. and finally to the calculation of vapor
pressure, The critical compressibility faclor at T. = I and 1', = I. varies in fact within a n:la-
tively wide rang~. as shown in thc data in appendix 1. Similarly. thc vapor pressure CUTVC5
for hydrocarbolls drawn for a system with reduced variables T.IT and In PIP, (Fig. 3.4) do
not m~rge into a unique line. but into a bundlc of quasi-linear curves. The values for the
critical compressibility factor and the slopes of the vapor pressure curves shifl in a regular
fashion with the length of the paraffin chain. or with molecular volumc. which is in this
case equivalelll. In order to beller characterize a compound. it seems necessary to intro-
duce a third charactcristic paramcter that takes thc$(: variations into account.
This is indecd what is done at the level of interaction energy calculation when we usc
the Kihara potcntial. It differs fmm that "f Lenn;ord Jones in that it introduces the term (/
to represent the molecular diameter:

- [("-d)"
e-4ct)- - -("-0)']
--
,-d ,-Ii
(3.8)

From this statement. several correlations ha.'e bcell developed that are distinctive in
their choice of this third parameter and the database from which they wcrc cstablished.
Indeed. it is appropriatc to specirlClllly state that if the basis for these correlatiOIlS rclies Oil
an acceptable theoretical basis-their developmcnt assumes the acquisition of experimental
data for. generally. volumetric and vapor pressure behavior, and sometimes cnthalpic
behavior. for compounds whose critical points arc known. as well as the value of this third
parametcr.
68

-<>.,

-1.5

-, T,O' 0.7

... u~.u Vapor pressure curveS of lI<pal1lffin$ (C1 - c.J in reduced


'"ariable$.

Allhough in principle these correlations apply (0 the estimation of residual terms in liq·
uid and vapor phase. the size of the tenns as they relate to the liquid phase (heat of vapor-
i/.alian.compressibility faclor.clc.) d«reases the pr«ision of Ihe calculation for this stale.
In general. we wilt have an advantage in calculalillg these values using corrchuiofUi that are
specifIC 10 the dense phase. We will give a few e~amplcs later on. As for Ihe most general
methods. in particular we die those developed by adopting the following Illl the third
parameter.
• the mlkal comp~iIilyfador
• Ihe lKenlnc fador. defined by the equation:
oo=-logIOP,"-1 (3.9)
where P," is the reduced vapor pressure for T, = 0.7.
This lasl parameter was introduced by Pitzer 11955J as a measure of the "acentricity- of
a molecule. Indeed. it is practically zero in compounds where the molecule is spherical
(rare gases. methane) and in paraffinic hydrocarbons. for example. it increases with the
69

length of the chain. The idea to introduce a third parameter related 10 the vapor pressure
curve in applying the corresponding slates principle is not limited 10 Pitzer. RiedcljI954]
proposed a parameter lhat has become known as the "Riedel raetor~:
d In P"

din T
for raT. (3.10)

Howeyer. the calculation of the Riedel factor requires values that are not readily avail-
able. and this proposition has nOllead to any important developmenlS.
The acentric faclor and the critical compressibility factor are related as shown in
Figure 3.5. and the equation proposed by Pitzer to represenllhis dependence is:
Z. = 0.291 - 0.08 ro (3.11)

We nOle. however. thai this correlation is not perfect. There is no similarity belween lhe
methods lhat is based on one or the mher of these two parameters (Z.. or w).

0.'

>J' 0."

j •
• •
.....
0."
f
.
~ ' '. •
0.27
• •• •
~ 0."'
...... ..
• • •
• • ••
~ • • •
" 02'

02< ,
0 o. , 0.2 0.3 0.' 0.'
Acentric IllClOr 0>

3.2.1 Correlations Using the Critical Compressibility Factor

3.2.1.1 Watson Method

A number of correlal!onS perlaining to the compressibility rador, the residual terms


of internal energy (II -lj°)lTr . enthalpy (11 - h')JT,. entropy (s - s')JT<. heal capadty at
constant pressure (c,.-4)1T,. and the fugacity eodficient have been established 1~lougen
70

/'1 (II.. 19591 based on data relating 10 82 componcnlS. laking into account a critical
compressibility factor nmge from 0.23 to 0.30. For values of this parameter thaI 3Te 1t:SS
th.m 0.26, some polar. and even some autoossociative compounds such as waler, were
included in the database. They certainly do not confonn to the strict rramc"'ork in which
lhe corresponding slate correlations should be applied. but form a rather important eXlen-
sianorit.
In general. the residual term is first calculated for a compound whose critical oompreM-
ibil'l)' factor is equal 10 0.27. A second order oorrection is tllen applied. which is propor·
lionallO tile dl."viatioll between the aclual ,'aim: of lhe critical oompressibilily faclor and
0.27. The proporlionality coefficient is a function of IIII' reduced variables T, and P,. For
properties of saturated phases. lhe residll/II lerms arc given as a function of lhe reduced
temperalure for several value~ of lhe critical compressibility faclor. From this correlation
....e comc awa)' with 1....0 characleri~tics: primarily thaI the "reference" value for lhe critical
compressibilily factor essentially corre~ponds 10 an average value that i~ valid al firsl
approximation for lhe mOSI common apolar compounds. The application of the correlation
at low critical compressibilily factor value~ wa~ made using dala for polar substances.
Ho.... e~>er. "'e should emphasize thaI this eXlension has no theoretical basis liS the corre-
sponding Slales principle is app[icable to apolar compounds only. and resulls in inaccura-
cies thai arc difficuh to .::valuate.

3.2.1.2 Radell Equation


In addition to the general correlations developed by Watson. it is appropriate 10 mention
an equalion for the calculation of molar volume of lhe saturated liquid phase proposed by
RackeH I [970J.Il is simple. precise. and in its initial form is ....rillen as:

,,, "CO)
(_". :(I_T,)l/1lnZ, (3.[2)

If ....e ell:press thc critical volume as a function of lhe criticaltcmperalUre. pressure. and
compressibility faclor.....e arri~'e atth.:: equivalenl form:

1;1.."= R;< Z)I ql_T,1"'1 (3.[3)



Its applicalion already results in satisfactory precision of 2.4% for a database of
36 hydrocarbons. However. il ....as proposed ISpcncer and Dllnncr. 19721 that the critical
compreSSibility factor be Subsliluted with a variable specific to this mClhod. tllc "Rackcl
compressibilit)· factor"·. Z Ilo' resulling in lhe cll:pression:

1.... NT, Z [I. (1_ 1'.1"'1


II = P -If" (3.14)

Table 3.1 shows the values of tllis parameter for several hydrocarbons. II may also be
estimated by re~'ersing tile preceding equation using a value for the molar volume in Ihe
liquid phase thai has been obtllined from elsewhere.
71

T.~.l.l

Rackcll "Ompressibility raclor. Z"" (Spencer and Danner. 1972!

Compound Z~ CompourKl Z~

Methane 0.2876 Ethylene 0.2810


Ethane 0.2789 Propylene 0.2785
Propane 0.2763 2-8uh,ne (WUlS) O.m,
II-Bmane 0.2728 bobulcnc 0.2727
!sobmane 0.2750 Cycloheunc 0.2729
/I·Penta"" 02M' Melh)'lcydohc~anc 0.2699
,,-Hexane
/I·Heplanc
0.2635
0.261 1
Ikn'...,ne
Toluene
0269'
0='
,,·Octane
,,-Nonane
0.2567
0.2637
Elhylbenzen.e
m.xylcne 0""'
OW"
,,·D«.ane 0.2466 p.xylene
0'"''
3.2.2 Correlations Using the Acentric Factor

Compared to the correlations that we have just discussed. the C':Orftlalions based on the
corresponding slales principle and utilizing lhe lin-lillie fado. lllI the thin! panuneter hll~'e
been renewed lind developed conslantly since the introduction of t~ Pitzer mdhod
(19551. They afe applied to the calculation or residuallerms. as well as 10 the equaliolls of
Slale. as we shall see later,
The acenlric factor is dcfincd from Ihe average slope of the vapor pressure curve com-
""red to a straight line in a system wilh variables T~/T and In (P.JP). Its calculluion
requires the knowledge or the critical point and the vapor pressure at a reduced tempera·
lure T, = 0.7. For most compounds.the data are available and Ihe vapor pressure is gcner-
ally known at Ihis reference lemperalure with satisfactory precision. The fact remains that
the definition of the acentric factor relies on dala whose values may vary as a funetion of
the precision of the e~perimen1al techniques. According to the database......e may find val-
ues for this parameler thai arc themselvcs slightly different.
If vapor pressure actually varies in a linear fashion in a system with variables TJT and
In (P.J Pl. the acentric factor may be arrived at using any vapor pressure dam. especially
boiling temperalure T~ at atmospheric pressure P~. We may then wrile:
P,
3 log 10 p:"
w__ ~-1 (3.15)
7 r.. _I
T.
l'his equation has the advantage of using only values that are readily available in any
database. but provides only one value approaching that of the acentric faa or. Similarly. to
the calculation of vapor pressure we may apply the equation:
po 7
loglo p~ =-) (I + al)
(T,)
T-l (3.16)

and obtain a precision Ihat is equivalellllO that of Equation 2.12.


·1
eS~lmjUl~[:

I 1

......." ... .... ilLJl'~..JIP... n I - ..


.
I u ti

U'I'_

o
DI
Jrl;

,.' '" 11."


.

_...1 _
,(r '..-.
('

rial u
....

I
I
I
I
o 'I - - -1- - - -1- -

57
.., ~.S =

~1.'D -- - - .-'- - -
I
I

-1.5 -+~~"i--~--""'*""I--"I1----+--.....--'li---I-~~""itIi""""""~=*"'~~r-----t---"
02 O. '0.6 l(l8 1 1.2 I 1. ",,[G, L, 2 22' 2.",

'.

I I I
I I •
--,-- I -.
I I I I I
I I • I I
- - I - - -, - - 1- - - I I
I I I I I I
I I • I I I I
- - I - - -, - - -. --~-----~------~--T---------r

I • I • I I
I I I I I
I
I
I
I 1 I
I
I
~---

I

'I --------
,I
I
- ~'- ~ L_ L ~_ ~---L~-i-___ _ __ L
I I I I I I
I I I I I r
J 1 1 _ __ l_ _ __ 1 L 1 L _
-2.S I I I
I I

o
74

which the oomponcnts aTC character;:.tcd by their dipole moments is. however. hindered by
the scarcity of e"pcrimental data. It is the same. a loniori. for aUloossoc;alive compound$.

3.2.2.2 Properties at Liquid-Vapor Equilibrium


Table 3.3 allows for the calculation of vapor pressure. the compressibility factor of the sal-
urated vapor phasc.and entropy of vaporization as a function of reduced temperature. The
following equations are used:
log IOP~ '" 'log lop:')tOI + w4(loglll p n (3.21)
Z v... '" (zV.")IO) -+- w~ I:" (3.22)
!},S" = ("-.1 10 )10) -+- W <11(os""',, llJl.<1&~loJ") (3.D)
In particular. it corresponds (0 an equation for vapor pressure in reduced variables:
4.318 1.454 0.3456
-logloP~= 3,209- ---r-
,
-+- Tr - r1
, ,
2.008 2.524 0.3981)
-+- w ( 0.1175 -+- - - -""""T'r -+- J (3.24)
T, T. T,

T.b1~ J.]

Correlation of propertics at 1IIIluration [Pitzer ~f QI.• 1955]

T, -(k>gwl,,~)(Qf -o(LQhP,") (Z~~)(fI) 4Z':" (As")(~i 0 1(6J") dz(6s")


, 0 0 0.291 -<0.08 0 0 0
0.99 0.02.5 0.021 0.43 -<O.OJ W '.83 0.6
0.98
'.97
0.050
0.076
0.042
0.....
0.47
0.51
0
0.02 ,
3.38 3.91
4.72 ...
0.'

0." 0.102 0.... 0." 0.D35 4.52 3.39 U


0.95 0.129 0.109
.'" 0.045 3 3." 0.'
0."
0.92
0.156
0.212
0.133
0.180
0.59
0.63
0.OS5
0.075
3."
6.23 '"
7-"
L3
,,.,
0.8
0.90
."
0.270
0.330
0.230
0.285
0.67
0.70
0.093
O.lIO
6.93
7.38 ,,,
853

0.86
O.S"
0.391
0.455
0.345
0.<03
0.73
0.756
0.125
0.135
8.19
aT,
10.3
11.2
'A'3
'82
090
0.522 0.475
0.~5
0.781
.""
0.140
,..,
'37 12.1 2.6
,.,.,
2.7
0.592 0.144
"
0.78
0.76
0.74
0.72
0.665
0.742
0.823
,
0.""
..,
0.620
0.705

0"'3
0826
.'"
0.8<»
O.ss,
0.144
0.142
0.137
0.131
10.57
U ...
11.84
12.49
13.9
14.9

"" ,.
2.'

•."
0.7

0.66
'.096
1.198
1.12
1.25
0897
0.911
0.922
0.122
0.113
0.104
13.19
13.89
14.62
18.1

'"
...3
2.6
,.
2.7

0.6< ..,08 1.39 0.932 0.097 ,,-" 21.8 25


,,,, ,-"
0.62
'.60
IAU>
1.70
0."
0.947
0.090
0.083
16.12
17.02
2J.2
24.6 "
2.3
• .38
• .36 ,.'"
0.'"
,...
,.ss 0.953
0.959
o.m
0.070
17.74
18.64
"-,
m
'.2

"
75

3.2.2.3 Lee and Kesler Method


The general method proposed by Pil7.Cr rests on the hypothesis that the residual properties
are, III a given reduced pressure and temperature. linear functions of the acentric factor.
This hypothesis was adopted by Lee and Kesler /19751 who developed a linear interpola-
tion of residual properties based on:
• those of the "simple fluid" (ro = 0). whiCh werc calculated usillS data for argon. kl)'p-
Ion. and melhane;
• those of a "heavy reference" fluid (w = 0.3978). n-octane. for which volumetric and
enthalpy data were available.
The volumetric properties of these fluids are repre$ented by a modified equation of
stale from Benedict. Webb. lind Rubin (see Chapler 4):

Z= I +.!!.. + ~ + ~ -+-
II, 1I, tl,
T;·l (P+ ~)"p(-l,)
, II, II, II,
(3.25)

where II, represents an adimensional form of the volume:

V=~
P,' (3.26)
, RT,
and is therdore found to be related to the compressibility factor Z by the equation:

z .P,-
II,
(3.27)
T,

Variables 8, C. D arc temperature dependent:


b z b~ h.
8=b\---Tr-TT (3.2tl)
T, T, T,
Cz cJ
C",c1--+TT (3,29)
T, T,
d,
D "'d l + - (3.30)
T,
Variables b;. c;. d;. {J. and yor this equation are or course different according to whether
we are dealing with methane or octane (Table 3.4).

T.bl~
3.4
Paramelen of lhe Benedict. Webb. and Rubin equalion (If ..ale applied
by ~ and Kesler 10 a simple fluid (<<>_ 0). and a referena: fluid (ID.., 03978)

Parameter Simple Auid Reference fluid Parameter Simple Fluid Referenet' Auid
b, 0.t18t193 0.2026579 0 0.016901
b, 0.265728 O.3JISll "'. 0.042n4 0.041 sn
b,
b.
""
0.15479
O,n:1032J
0,0236744
0.0186984
0.0.21655
0.203488
D.OJI J3I1S
0.0503618
,, .
](f·d(
Io'·d.
0.15S488
0.623689
0.65392
0.060 161
0.48736
0.0740336
1.226
0.03754
76

The method applies to residual properties at given pressure and temperature. com-
pressibility factor Z. enthalpy (h - h')JRT. entropy (s - ~)lR. heal capacity 81 constant
pressure (cp_c;)lR. and the fugacity coeffICient. The range covered for pressure and tem-
perature according to the authors is as follo-.;;

0.3<lir, .. 4 O"'P,"-lO.
Calculations are carried 0111 by:
• dctennining the reduced variables of the nuid \0 which we want to apply the
method:
• determining. using the equation of Siale for residual properties (compressibility fac-
lor. for example) of the simple nuid ztO) and of the reference nUld 21') corresponding
to the reduced variables:
• performing linear interpolation:

z = ZIOI + ;,j (Z") _ Z(O» = ZIOI -+- wt.Z (3.31)

As an example. Figures 3.8 and 3.9 show the compressibility ractoc of the simple nuid
and the coefficicnt~.Tables A2.1 to A2.1O (Appendix 2) provide the corresponding val-
ues for residual quantities (enthalpy. entropy. heat capacity at constant pressure) and for
the fugacity coefficient.
The calculation of vapor pressure may be accomplished by application of the equilib-
rium equation (equality of the fugacity in the vapor and liquid phase).

, ,,
,
, ,
-- - - T;:: 0.8- -- ~: __ ~.9_ t!.~_ 0.lJ,t-~~~.~C~·~·;·~·:·3;:·~·~·~·;·~
08
-______ !.:1 _
, 0.8
, 1 I 0.1l6I
, 1 I 1
, 1 , 1
OA - - - - - -,- - - - - - r - - - - - ,- - - - - -,- - - - - -
, 1 , 1
, 1 , 1
______ ' L .J 1 1 _
0.' , 1 j 1 ,1
, 1 1 I
, 1 I 1
0
0 0' 0.' 08 0.8 ,
Reduced pnlSSUre

t1p~ 3.8 Calculation or the comprcssibility fllClor for lhc simple fluid zlOl
usinlllhe Lee and Kesler method.
77

0.1
,I ~-----~------I------~---

I I , t 1: ... I."
,,
, I
, I
, j '

o -j",.. 1.
, 1
•-<>.1 ,- - -- - - ~ - - ---
, "
,T,_0.8
" , "
I , I • ,
- - - - - -,- - - - - - r - - Q.lil. -0-92 - - - - -,- - - - - ~ - - - - --
I I " 0,94 0.96 1 0.96 '
• , I I *
, , I I ,

-<>.3+----j---t----+---I---+-----j
o 0.2 0.4 0.6 0.8 1.2
Redl.lCed pressure

F11"'~.\' Calculation of the oomprc:ssibil,ly (actor


using IIII' I..cc and Kesler method: oorrC(."lion lerm 62.

Ho,,·cver. the authors suggest using lhe following equation:


6,09648 6
In p~ = 5.92714 - - 1.28862 In T, -+ O.I68347T,
T,
(3.32)
15.6875
+ru ( 15.2518-=:;;.'-0
T,
13.4721 In T. + 0.435 77 T~)

This last equation may also be applied to Ihe calculation of the acentric faClor if we
know dala for the vapor pressure.
There is not an exact equivalence between the vapor pressure resulting from Ihe equal
fugacity condition with fugacities calculated using the ue and Kesler method. and the
resull from Equation 3.32. At low reduced temperature. the differences are small and
ineonsequentiaL On the other hand. on~ the reduced temperature surpasses appro)l;i·
mately 0.98. the value resulting from Equation 3.32 does not allow for the calculation of
saturated vapor densities as the equation of state for the reference fluid has no root corre-
sponding to that phase.
The Lee .nd ~ler method may abo be applied 10 mb:lures by ddiniac "pseudomlj.
caI~ wriabla (see Section 3.2.3.2). The precision is very satisfactory ror the calculation of
residual properties and. while maintaining its principle. we can adapt it to other problems.
However. prudence is advisable when we are talking about fluids whose acentric factor is
clearly higher than that or the reference fluid (0.3978). We then find oun;elves extrapolat·
ing with respect to the database that allowed us to develop the method. and it is difficult to
appreciate the accuracy of the results. Of course. the method is not valid for polar com-
pounds. at least in its original form.
o EXAMPLE 3.2
Calculation of the isochoric change of a fluid
We shall determine the pressure change in a bollie of liquefied gas as a function of
tcmpcralUre. Wc considcr two cases: fiT!it. a bonle. with a capacity of I liler-conlaining
314.6 grams of ethane: and second. a boule with the same capacity that contains only
113.24 grams of ethane. The range of temperalUre goes from appro~imately 0" to
6O"c.
The first point to e~amine is the state of ethane in the bollie for temperalUres less
than the critieal temperature. If two phases 8re prescnt.the preSSlIre is eqllalto the
vapor prcssllre. and we can calculate the proportion of liquid phase. If there is only
onc phase. the pressure will lhen be dctennined using a Z(T,. P,. (») correlation. As
the range of temperature e~tends beyond that of the critical temperature. we shall
certainly eneOllnter th is last correlation.
For a two-phase system. the proportion of liquid phase is detennined by balancing the
volume. which is the given property. We will use the following notations:
N, : total number of moles
NI. : number of moles in liquid phase
N I ' : number of moles in vapor phase
V : total volume
v : overall molar volume (v '" VlN,)
.J~": molar volume in liquid phase
vv." : molar volume in vapor phase
X : proportion of liquid phase
We may write:
NI'+NY",N,

NL"L."+NYvV.,,=V

and derive from it:

The proportion X nlust be between 0 and I. If it is negat;l·e. the system is homoge-


neous vapor. If it is greater than I. it is homogeneous liqllid.
What remains is to choose a way to calculale the vapor preSSlIre. and the molar vol-
ume in the liquid and gas pha~. For the vapor pressure. we usc the Lee llAd Kesler
correlation (Eq. 3.32). The compressibility factors and the molar voilimes will also be
calculated using this method for the vapor phase. but by IIsing the simpler Rackell
correlation (Eq. 3.14) for ttle saturated liquid phase.
We shall usc the following data:

T<=305.4K. P<: 4.88 MPa. (»:0.099. ZII»=-0.2789. M",30.1g·mol- 1


The total number of moles is equal to N I =- 314.6130.1 '" 10.45 moles for the first bot-
tle. and N. =- 113.24/30.1 '" 3.76 moles for the SCl:ond bottle. The given volumes are
respeclively VI '" 1.000 /10.45 '" 95.69 eml/mol and vl '" I.CXXlI3.76 '" 265.6 em l fmol.
Ji_ dlll_-_
-.1.

1' I

....L
UI r 'or·
.
. , 1'--
.
,

U~' d h
.10' ,.
a

1=1.-

'f"

If
"4'

II

reSll~lt::: P

th

- , p

1
L
11
1
L
1.1

u
.

1-
1-

28 I

,0 -
II-
I

~mD-ouln--

It
82

10 determine residual quantitIes as a function of the critical compressibility factor


(Seclion 3.2.1) as .....ell as for the second vinal coefficient. 'Ille first problem c"countered is
to characterize such compounds. The parameters used up to this point (critical points-crit-
ical compressibility faclor. or acentric faeWT) arc themselves sensitive to polarity and
aUloassociation by hydrogen bonding.l'hcir values dearly deviate from tile correlations
Ihat may be put forth for lhe h)"drocarbons as a function of molecular weight. for example.
The choice of dipolar moment turns oul 10 be deceptive. Finally. the experimental data,
when Ihey exist. 3rc oflen limited 10 vapor pressure. density in the liquid phllSC. and possi·
bly 10 the second virial coefficient. Howc\'cr. it is appropriate 10 cile Ihe work of Stid who
introduced a "polarity factor". analogous to the acentric factor. starting from the vapor
pressure dctermined at a reduced temperature of 0.6:

(3.33)

The method has been applied to the calculation of molar volumes of the saturated liq-
uid phase /Halm and Stie!. 19701 and then of the compressibility factors ror the vapor and
liquid phases [Stipp (/al.. 1973. Halm (/ ul.. 19851 "ia the equation:
Z = 2(0) + wZ lJ ) + XZ m (3.34)
where values Zlof, zt 1l, etc.. are functions of the reduced variables. Finally. more recently an
extension to the Lee and Kesler method has been proposed that includes a third rderence
compound, walcr [Wu and Stie1.1985I, for which the properties lire represented using the
Keenan and Keyes [19691 equation of state,

3.2.3.2 htension 10 Milltures


Although we ha\'e not yet approached the sUbjtm of mixtures and the calculation or their
thermodynamic properties. we shall present here the S<Kalled method or "pseudocriticar'
variables (or properties),
The compoosition or a mixture is known by the mole fraction of each romponent. We \\.;11
consider the mixture as a pure substance whose critical properties (and possibly the acen·
trie factor) are obtained from the same properties of pure substances using the rules of
empirical weighting. We can therefore calculate the reduced variables of the mixture using
the methods de\'elOfl'.'d for pure substances. namely their residual quantities: compressibil·
ity factor. residual enthalpy, etc,
First. we shall consider the case of correlation of corresponding states of two parame·
ters (critical temperature, and critical pressure). The most simple of the rules of weighting
[Kay. 1936] is linear:
(3.35)

""here ~; denotes the mole fraction of component ;.


We may also apply such a linear rule to the acentric factor.
The results obtained in this manner are generally acceptable. especially for the vapor
phase. taking into account the simplicity of the method. Of course, the -vapor pressure of a
mixture" cannOt be calculated in this way since for a mixture. at a gi\'en temperature. the
limits of the two-phase range (bubble and dew point pressure) do not ha\'e the same value
83

and the liquid vapor equilibrium can be calculated only if we can measure the contribution
of each component to the Gibbs energy of the phases in equilibrium. The fugacity coeffi-
cient of Ihe mixture that is detcnnined by applying the method of p$eudocritical variables
may therefore not be directly applied [0 tile calculation of the equilibrium. and represents
only tlie residual property of IIie mixture.
The Lee and Kesler method can be applied to mixtures. The authoB recommend the
following mixing rules:

(3.36)

(3.37)

(3.38)

where; (3.39)

Z<,I = 0.2905 - 0.085 w, and Z..... = 0.2905 - 0.085 ro.., (3.40)

(3.41)

3.2.4 Conclusion Concerning the Corresponding States Principle

The calculation of thermodynamic properties vcry often depends on the corresponding


Siaies principle either explicitly_ as when lhe Lee and Kesler melhod is applied. or implic-
itly when ....e use the equlltion of stale for which parameten; are correlated as a function of
reduced temperalUre and the acentric factor, for e~llmple. This law is applied fin;1 and fore-
mOiSllO pure subslances but. in faci. it has been extended to mi~tures. Ulilizecl...-ilhin rell-
500llblc limits, il is 01 inelilimllble n,loe. J!o",'uer, il Is otcIvisable 10 be ."'..re 01 exlenswn
misUSe". II nuay nol be IIpplied 10 polar .,.,mpounds.. Ib ""'Iension 10 .,.,mpound~ 01 hillh
molecular ""eighl Is IlUbJed 10 (>/Iulloo lind il k IIppropriale In Ihls cue 10 analyze Ihe
molet:ubu inlenldions in lenllS 01 interad;ons ....I...een the C'OlllililltCnlllTOUpIi ollhe mol·
«uk. Of course, in Ihis cue "e ml1\l also lake inlo lI«ounl the size IIIHl sope 01 the mol.
«u~ We must also remember that wc do not always make use or the necessary parame·
ters (critical properties) either because they have not been measured, or because they are
located in a temperature lOne where the molecule dissociates. II is therefore necessary to
predict them. for e~ample. using the structure correlation properlies. We shall provide
some examples. Such predictions do nOl generally impro\'e the precision of the correspon-
ding stales principle. We must. however. whene,"er possible. validate ;b application using
available experimental values.
3.3 STRUaURE PROPERTY CORRELATIONS

The observed change of the value of a property of oomponenlS in a homologous series


(n paraffins. aromatic alkyls. primary alcohols.etc.) with the length of the chain is an exper-
imental fact that naturally tends to break down the value of this property in OOl1\ribulions
that are attributed to the constituent groups of the molecule. Having established this rela-
tionship. we are now in a position to predicllhe values of the given property for new molec-
ular struclures made from the same groups. It is a forceful approach. Indeed. the number of
groups thai we find in Ihe area of organic chemistry is incomparably more restricted that
the number of distinct. chemical cnlities. Depending on the property in question. it is used
with more or less success. We shall offer some examples that relate to quantities already
encountered. but we shall later apply this method for calculating the deviation from ideal-
ity (Chapter 7) or for predicting thermochemical properties (Chapler 13).
It is necessary to first specify certain easily ullderstood limits. III general.thcsc methods
are poorly applied to the first members of homologous series. loey are oftell considered a
special group. This restrictioll is not serious as long as it illvolves only properties of pure
substances and not mixtures. Indeed. the properties of these compounds are generally well
known. We may not. however. use them to develop laws that are particular 10 the homolo-
gous series to which they belong as ~individual~ members.
Furthermore. insofar as it is possible. we must include ~the proximity effect"". The
constituent groups of a molecule are not isolated. A definition that is too narrow and
would neglect the inOuence exerted by proximity would cause gross errors. We know. for
example. that the hydroxyl groups of aw.diols are nOI independent. and characteristic of
the alcohols. they are separated by numerous CH 2 groups. A fortiori. it is impossible to
separate II polysubstitUled carbon in autonomous groups. Like Benson et at [19691. there-
fore we must always define a group by the nature of the central atom and of those atoms
immediately surrounding it. [n this way. for example. the methylene group of a linear
paraffin e-(Ch (H)2 will be differentiated from an alkylbem:ene [C-<C..)(C)(H)J.
where COl sllmds for the aromatic carbon. The disadvantage of such a description is obvi·
ollSly a considerable increase in the lIumber of groups. and thereforc the length of the
cxperimcntal database used to evaluate the contributions of each group. [n addition. for
polyrunetionalmoleculcs. it turns out to be insufficient. The interaction betwcen two runc-
tions may excn itself even if these two functiOfls are separated by a methylene grouping.
We must also discriminate between the cis/trans isomers. and the ortho. meta. and para
configuralions of the aromatic nucleus. etc.
Finally. the general characteristics of Ihe molecular structure (volume. shape. cyclic
structures) are only taken into account indirectly. This way. extrapolation to long chain
hydrocarbons appears often imprecise. sometimes nonsensical. when confronted with
experimcntal datll..
In addition. we mUSI distinguish group contributions when they are applied to the ideal
gas properties or to real compounds. [f molecular interactions do nOI exist. we may more
reasonably attribute to each group a contribution of its own.loe entirety of these contri-
butions will fonn a charaClcristic vector for thc property in quC/;tion. On the other hand. if
we must include the cohesion forces. we shall SUbslitute group interactions for molecular
interactions and end up with a characteristic matrix.
85

Such will be the case when we introduce the UNIFAC (see Chapler 7) method of calcu-
laling deviations from ideality in the liquid phase. for example. It should undoubtedly be
the case for correlations concerning critical points. the heal of vaporiulicm. cle.
These questions were recently the subject of a synthetic investigation [Gani and
Conslanlinou. 1995] and new approaches thai depend on a more precise investigation of
the geometry of the mol~ule were proposed /Constantinou lind GanL 1994].

3.3.1 Properties of the Ideal Gas

Thermodynamic statistics allow us 10 build the ideal gas partition function from the ener-
gies of translation, or rotation of all or part of the molecule, and the longitudinal and trans-
versal vibrations of the interatomic bonds. The required parameters for applying the
obtained expressions are molecular mass. the moments of inertia of the molecule and of
the constituent groups. and the Raman or infrared absorption frcquencie$. Those relating
to molecular geometry (bond angles and lengths) are characteristic of atomic groupings..
As for the absorption frequencies. we know that. as a first approlOmatKlIl, they arc related
to the nature of the bond in question and lillIe sensitive to the environment. It is therefore
natural that the thcrmodynamic properties of the ideal gas. molar heat capacity. and the
entropy reported at absolute zero, may be broken down into group contributions.
For molecules or groups. the possible symmetry of certain structures may render several
distinct configurations indistinguishable. For example, such is the case for the three posi-
tions of the methyl group due to a 120" rotation around the C--e bond, or even the twelve
positions of the methane molectlle that are also obtained by a lZOO rotation around one of
the four G--H bonds. It should clearly be taken iOlO account in the description of a prop.-
erty such as entropy that is related to the "degree of order"' of a system. This symmetry is
expressed by the "degree of external symmetry" and the "degree of global symmetry" of
the molecule, The degree of external symmetry f1 is equal 10 the number of indistinguish-
able positions that the molecule may aS$ume by simple, fixed rotation on itself. Its evalua-
tion is facilitated by the usc of molecular models. Table 3.8 provides the values for wme of
their structures.

Table J.8
ArnouDl of external s~mrtM:try for some compounds

Compound •, Compound •
,
BUlene I
Ethanol ,, Methyl chloride
Trich Ioroacelonitrilc
,3,
Teniary butanol
1.3 BUI.diene ,, Paraxylene
Ethylene
''''''''~
Orthoxylene , Anthracene
l.J..5 Trimethylbcnune
•6
Metaxylene !Jenzene
lsob!Jlane
Ammonia ,
2
3 Neopcntane
Carbon lelraehlo<idc
""
"
86

Global symmctry.s.csscmially differs from it by rOlation of the methyl groups. We Slale:


s = a3~ (3.42)
"'here 11 is equal \0 the number of methyl groups in Ihe molecule. Certain correlations
incorporate the symmetry of these mctllyl groups into their contribution. and specifically
their external symmetry only.
finally. we are led to introduce certain corrective terms reJatcd 10 cis/trans isomerism.
or to the position (orillo. meta. para) of ,II<: substitutions on the aromatic nucleus.
We h3\-C:

(3.43)

(3.44)

using.6 and fj: to designate tile ooniriblllions and the corrective terms thai rel11le to heal
capacity and entropy respectively. N j is the number of groups of type i. and N, the number
or oorrectiolls of type j.
Table 3.9 provides an example of such a correlation. limited to hydrocarbon structures
[Benson f!/ uf.• 19691. They are also valid for groups containing double bonds, triple bonds.
for halogen and sulfur derivati\·cs, the alcohols,cthers, ketones, amines, and the nit riles.

Titbit: 1.9
Group COfltribulioos in tile calculation of molar
Ileat capacity al eOlmant preMure and of molar enlropy.
Standard SIDle: ideal gas, p" .. I oor. temperalure 298.15 K [lkrlSOO rr "I.. 1969J

Groups
,,;
(cal)
.-
(ul·K-I,

C-(C)(H)J 6.l9 30.41


,.'"
(;---{(;):(I·I),
C---{CM~I)
(;---(C).
•."
4.37
9.42
-12.07
-35.10
(;..---(C..l, (H) 3.24 11.53
(;..---(C.. I: (C) 2.67 -7.fR
C-(c..) (Hh 6.19 30.41
C---(C..) (C) (H)~ 5." 93
C---Cc..l (C), H . .8 -12.2
Each orlho interaction L12 _\.61

We may also cite the method proposed by Rihani and Doraiswamy [19651. The method
gives the group conlribution in the form of a polynomial function of the temperature
(cio" /l + bT + cT~ + dT). Thble ].10 shows some e~amplcs. The group definitions are less
detailed than Benson's work. but because of this fact. the application of the method is sim-
pler and the risk of error less.
87

Table J.Il}
Group OO<llributiQns for tlte calculation of mol.. heat capacity al COflS\.llnt prt$Sllr...
Standard Slate: ;(I<,al gu. PO. I bar [Rihani arKl Dorais.... my,I96S]. Units: <11.1· mol-I

GroUp5 ,. (\b·IO' <\<"-10' &/·10"


CH, O.~7 2.143.3 -Q.O!I$ 2 0.1133
CH, 0.394 5 2.1J6J ...{l.1197 0.2596
CH _3.523 2 3.4158 ...(J,281 6 MOL S
C -S.ll307 4.454 1 -tl420 8 1.2630
C.H -1.4572 1.9147 411233 0.298 ,
C.. (I) -1.38ll .3 1.sIS OJ -0.106 9 0"'" ,
C. (2) 0.1219 l.2170 -",." 0.2122
(I) Aromoli<: carbon bound to an aromatIC carbon and an a~ph.til: carbon (toluene).
(2) Aro""01'" corborl bound 10 two aromatic carbon. (naphlalcne).

o EXAMPLE 3.3
Application of the Benson, and Rihani and
Dorsaiswamy methods to ortho ethyl toluene
We shall calculate the molar heal capacity and entropy of orlho ethyl toluene at
the standard state 8t 298.15 K. The ...alues from the literature are. respedivcly.
37.94 cal, mol-I. K-I and 95.42 eal· rnol- 1 . K- 1.
First we shall use the Benson method.
We specify:
• four aromatic carbons bound to tWO other aromatic carbons and II hydrogen:
4· [C..-{C•• MH)]:
• twO aromatic carbons bound to two aromatic carbons and a paraffin carbon:

• a pllrllffin carbon bound to an aromatic carbon and 3 hydrogens:


l ' [C-{C..)(H)3]:
• II paraffin carbon bound to an aromatic carbon. II paraffin carbon. and two hydro--
gens:

• a paraffin carbon bound to another paraffin carbon and three hydrogens:


1 • [C-{C)(Hhl:
In addition. there are two methyl groups whieh we will take into account in calculat-
ing the entropy term (symmetry term).
Finally. we will introduce the onho interaction correetion.
Therefore. we arrive at the following calculation (Table 3.11):
8'

TableJ.U
E!Ulmple orille application of tile Benson method 10 Ihe cakulation of
heal capacity aod entropy for onhoclhylloillene

Groups lJ,e; U N
C. (C.h(H) 3,2~ 11.53 ,
jC..-(C.. )lCC)1
IC-(C...Ht1hl '"
6.19
-7.th
30.41 ,,
2

C-Cc.,)(C)(H)l
C-(C)(Hh '"
6.19
,.3
30.41
_ 4.4
,
Symmcny (-R In 3')
Each orilla int.:racl;on 1.12 _1.61 I

The calculation of heal capacity and entropy shall be performed using Equations 3.43
and 3.44. From thc preceding table. we obtain the following values:
c;",37.64ca]·mol- I ·K-l and ~:94,85caJ·mol-I·K-1
We again perfonn the same calculation using the Rihani and Doraiswamy method.
Table ],12 below summarizes the calculations.

Tabl.,J.12
Group oonlribul;0n5 in the caklilation of
molar heal capacity at ron~lanl pressure and molar entropy.
Standard stale; ideal gas. po '" 1 bar (Rihalli arK! Doraiswamy. 19M]

Groups • b·IO" ~·10· d·lO~ N

C.H
C.. (1)
-1.4572
-1.3883
1.9147
1.5159
--{}.1233
--{}.I06 9
0.2985
0.2659 ,•
CH, 0.6Ol!7 2.1433 --{}.os.s 2 0.1135 2
CIl.. 0.3945 2.136 3 --{}.1l97 0.2596 I
o,clhyholuCRC ---6.9935 17.1135 --{}.m I 2.2124

These results lead 10298.15 K. at cp '" 35.74 cal, mol-I. K- 1.

3.3.2 Critical Coordinates

Knowing the critical properties is an absolule m~~essity ea~h time we wish to apply one of
the correlations of corresponding states. This means that we arc forced to fill in the gaps of
the literature by proposing prediclive methods that. for the most part, themselves rely on
group contributions. Simmrock elol. [l986llisls fifty-siJl methods For the calculation or
critical temperature. fifty-five for critical pressure. and fifty-rour For crilical volume. and
determines the precision for most of them. The choice is considerably more difficult in
thai. depending 011 the family (hydrocarbons. ketones. alcohols. etc.), one or the OIher of
these methods seems preferable.
69

We shaillimil ourselves to the description of the method proposed by Lyderscn 11955].


which, laking into acoounllhe precision shown by Joback [19841. is considered one of the
best. It may be applied to hydrocarbons. halogenated derivative$, alcohols. ketones., alde-
hydes. acids. esters. amincs. nitrites. Ihiols. and mcrcaptans.
we use the following equations:
h
T = 0.51l4 -+- 0.965
Tr
~ N;AT; _
i
(LI
NjA T I)' (3.45)

p. (bar) = 0.113 -I- O.OOJ2n - L, N, API (3.46)

(3.47)

where llT. M>. and t.v stand for the increments allribulcd to the constituent groups for the
cakulalKm of temperature, pressure. and critical volume. Tb Ihe boiling point al atmospheric
pres.~ure. and Nj the number of groups of type i in the molecule. Table 3.13 shows the incre-
ment valm."5 for the main hydrocarbon groups. A complete listing is given by Reid 1'//1/.[1987].

Table l.U
Contributions of h)"drocarbon groups 10 critical properties [Lyderxn. 19551

Groups or AP ,V
(K' (har) (c;ml·mol- l )

Aliphatic Groups
-0.0012
-CH J
-CH l -
0.01~1
0.0189
0.0164
0 "
56
>CH- 0.0020
"56
>C<
=Ctl l
=CH-
=c<
Cyclic Groups
0.0067
0.0113
0.0129
0.01l7
0.0043
-0.0028
-0'<006
0.001 I
..
27

36

-CH I - 0.0100 0.0025


>ClI-
>C<
0.0112
0.0042
0.<XXl4
0.0061
'"
36
27
_CH_ 0.00!l2
0.0143
0.0011
0.00l1l "
=c<
"
We note lhat for the calculation of critical temperature. the normal boiling point mUSI
be known. This is a disadvantage since this property is sensitive to structure (configuration
of the hydrocarbon s1r:eleton. among olher things) and is difficult to predict. 1'he Joback
method contains group conlributions for this property. but the results are or "ery variable
precision [Reid ell/I.• 19871.
The method proposed by Ambrose [1978. 19791 is of comparable precision. but is more
complicated to apply. It is explained in detail in the work by Reid et /J/. {1987] and. like
Lydersen.covers a large number of functions.
When using the group contribution correlations. we must be wary of lhe misuse of
extrapolations. The calculation of critical properties is an ellample. T50nopoulos /1987]
90

demonstrated llial the blind application to II paraffin containing 100 carbon atoms resulted
in a negali~e reduced temperature using the Lydersen method. and that the two methods
by Ambrose and Lydencn deviale from cllch othcr starling from C:!o hydrocarbons.

3.3.3 Calculation of Molar Volume in the Liquid Phase

We could cite many other examples of calculating the thermodynamic properties of pure
sub!itances by group contribution,The breaking down into groups proposed by Benson has
been applied to the calculation of properties in the liquid phase by Domalski and Hearing
[1988.19901·
An especially simple method was proposed by Elbro et al. [1991 J to ohtain the molar
volume in the liquid phase Wilh reasonable precision.

3.4 EXAMPLES OF THE RELATIONSHIPS


BETWEEN THERMODYNAMIC PROPERTIES

We have seen that applying the corresponding states principle requires that we know the
critical propenies. This disadvantage is nOi small as these data are sometimes unavailable.
The value for the normal boiling temperature. vapor pressure values. and density Finally
make up a more readily available database. A simple example will demonstrate that these
values may be combined using the equations that we have given to supply the missing (;nt-
i(;al data. More systemati<:ally. a group of empirical equations wilhout theoretical basis but
with reasonable precision may be used to advantage.

3.4.1 Calculation of Critical Properties


from Vapor Pressure and Density Data

It often happens that we have at our disposal data such as vapor pressure or density. but
nOl the critical properties. In this case. we may assess these "unknown" values that. with
the use of the corresponding state correlations or the equations of state. concur with avail.
able data [see. for example. Rogalski el al.. 1992: Vetere. 1987. 19891. We shall provide a
simple example of sueh a calculation.

o EXAMPLE 3.4
Calculation o( the critical properties (Or n-butane
We have the melll\ured vapor pressures and "molar densities" of n-butane at ere and
I at 100"C. The results are listed below.
91

T.ble 3.14
Molar diollsity and ""por prc:ssurc or ,,_bulan.r:

T~mperallue pC. P"


(oq (mol- cm- l ) (bar)
0 1.035 10-1 '.036
'00 8.010 lO-l 15.28

The correlations that seem best adapted to this calculation are the RackclI equation
(Section 3.2.1.2), and the simplified exprcs.sion for vapor pressure as a function of
reduced temperature and the acentric factor CEq. 3.16).
We write the RackclI equation:
10
v~;oTR.
R7~ZII.(I-T,""'1 (3.14)
,
in the form:

where application at two temperatures T, lind T1 yields:

.".
,
vL"
[(
"_'_,,, T)~
1 __1 -
T,
( T)~] InZ
1_...1
T, ~

The Rackcu compressibility factor will be estimated using the equation:


Z/lo - 0.29056 - 0.087 75 (j}
in addition. we have:
vL."= IlpL."
so thai for the acentric faClor we oblain the following expression:

To use the vapor pressure dilla. we usc: the equation:

10&10'><> "'_~(I-!-W)(T'_l) (3.16)


P,. 3 T

0"
92

In this way we have tWO independenl expressions for the acentric factor as a function
of critical temperature. By making 11 series of assumptions about this temperature we
shall determine the value nppropriolc 10 each expression. as shown in Table 3.15 below.

Table ,'-15
Calculation of ll>c ~ntrk flOCtor us • fur>ction of as5umpllons
made about ll>c critical temperature of ,,·bulane

T
(K)

(Roeken)

(Eq.3.8)
0.21636
""
,w
-o.9101J
-0.40071
O.Ol] 81
O.24S2J
0.21558
"0
O.ln2l 0.22013
'" 0.20128
'"
'"
'30
0.20836
O.243'T1
0.311120
0.19846
O.Ill732

We thus find T< '" 424.8K.a value in linc with the experimental value (425.18K). From
this value. we have the values for critical pressure. 37.34 bar (exp: 37.37 bar). and the
acentric factor: 0.202 (exp: 0.199).
We must nOle thaI we are dealing wilh 11"0 setS of different data: vapor pressure and
density. Vapor pressurc dala. although morc plcntiful, would havc certainly deler-
mincd the curve for vapor pn.'Ssure. bUI not 'he final poinl of this curve. which is the
crilical poinl.
The "models" used must be understood 10 be valid within the range under considera-
lion. If the vapor pressure data had been at low temperature (below the normal boil·
illg temperature). Equation 3.16 CQuld have produced gross errors.
We may also use an equation of state that is able to simultaneously show the vapor
pressures and the volumetric properties in the liquid phase, and whose parameters
are a function of the critical properties and the acenlric factor. such as the one pro-
posed by Schmidt and Wenzel [19811. The Lee and Kesler model discussed above
lends itself cs~iaJly well 10 such an evaluation, However. we must point out that the
CQmpounds for which Ihe critical properties are unavailable are generally located OUI-
side of the normal range of application of equations of state and the CQrresponding
states principle. As they arc in fact considered intermediary parameters., critical prop-
erties that are calculated in this rashion must be located within a temperature zone in
which lIclllal calculations will not be carried OUI.

3.4.2 Calculation of the Heat of Vaporization: Watson Equation

It is desirable to also provide;\I1 example of Ihe Watson equation t1931. 1943].11 allows ror
the calculation of the heat o( vaporization ah" at any temperature provided that al any
particular temperature To. the vlllue of this property is known.
93

II is wrillcn:
(3.48)

The exponent 0.38 is absolulely empirical. Wilh Ibis method, the known value for heat
of vaporization serves 10 improve the prediction founded on Ihe reduced lemperfllurc. It
was modified byThd:: and Slicl]I966. 1967].

3.4.3 Empirical Equations Developed from


the Normal Boiling Point and Density

A cerlain number of empirical equations were proposed for the calculation of thermody-
namic propenics Slaning wilh llle normal boiling point and the density. Their accuracy is
milled. their basis 10lal1y empirical. and their range of application limited (0 lhe hydrocar-
bons. but Ihey have merit in that they require only data Ihal are generally available. We
will mention those developed by Riaz; and Daube" (1980.19871.
Example: X'" (J T b'" p~ (3.49)
where T b is the normal boiling temperature expressed in Kelvin. p is Hspecific gravity" al
WE meaning Ihe density al 288.7 K relati"e to water at the same temperature. X Ihe prop-
eny in question. such as the molecular mass.. critical propenies.. critical volume. molar vol·
ume in Ihe liquid phase al 2O"C at almospherie pressure ..,L. heat of vaporization l!Jla. and
the heal capacity of the ideal gas al O. 600. and 1200"F (255. 590. and 920 K). Of oour.;c. Ihe
numerical values of the ellponenlS III and n dcpend on the propeny in question. They arc
provided in Table 3.16 along with the average deviations noted by the authors. This method
has been recently ellpallded to oompounds of high molecular weight where the boiling
temperature at atmospheric pressure is unknown. After a comparative study of several
calculation methods for the critical properties and the acentric factor, Voulgaris l!/ al.
fl99IJ reoommended the Riaz' and Daubert method.

T.~J.16

Param<:tus of the Riari and Dauben colTelalion applicd 10 the calculation 01 molar rna",
rnlic.al poinls. density. hcal of \"llporilation. and Ileal capacily

Devialion
Propeny Uniu m
" " (%)

,.,
M 8m<>< '
,,,
K
1.66/)710 <
19.0623
2.t962
0.588"
_I.ot64
0-""
2.'
U
P, 5.53031 10' -2.3125 2.320 I 3.1
emJ·mol- 1 1.7842 10-< 2.3829 -1.683 2.8
", em J . mol-I 2.6594 10-< 2.1262 -1.8688 2.8
"
p s/=' 0.983 719 0.002016 1.00s5 2.8
"".
",(O'F)
J ·mol"
J 'mol-' K-'
38.-1502
8.134410- 0
1.1l47
2.6n4
0.0214
-2.363
I.'
3.'
J 'mol-' K-' 85n IO-J
<A600°F)
<,,(IZOO"F) J·rnol-'K-' 1.421 10-< ,.385,
2.4219 -1.9-136
-1.932
3.'
4.2
, I~

"
D
"

I,
U-.,

1,

'-
c·· C- ,5·'0,'
,
, ,-

II
95

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33.2OilO-2llO.
Vetere A (1987) Methods for cstimation of critical "olume5- Tht Chemic/<f £Ilsinurins J•. 34, 151-153,
Vetere A (1989) Estimation or critical pre5SurC!l hy tl>e Raeken e!juation. Chm,. Eng. Xi.. 44, 791·
m.
Voulgaris M, Stamataki, S. Mag<>ula. K. Ta$liios 0 (1991) Prediction of physiclll propenieli for non·
polar C<lmpounm.. petroleum and coal liquid frllClions. fluid {,""$I! EqIJilihrill, 64. 73.1{)6.
Watoon KM (1931) 'mi. Eng. Chrm.. 23,360.
97

WatKKl KM (1'M3) 'nd. £"8' Chtm.• 35.393.


WU GZA. Stiel1.1 (1985) A generalized equation of state for tile thermodynamic properties of polar
"uids.A/CIl£ 1.,31.1632-1644.
Vaws CL. Yang HC, Hopper JR. Cawley WA (1991) EqualK'" for liquid density. lI}'droctl,bm,
Proce:uing. January. 103-106-
Vu J. Eser S (1M) Iktcrm;1I3tion of critiral properties (Tc _Pc) of IlQmc ~I fuels. Ind. £"8. Cht'm.
Rt'~ .• 34. 404-4(l9.
I
4 Equations of State

The equations of Slale express by means of a mathematical expression:


£(T,I'Y.N) ~ 0 (4.1 )
the relationship bclwcen the temperature and pressure. volume occupied. and the amount
of mailer for a pure subslancc or mixture. This «Juation is more often reduced to one
mole:
dT.I'.u) = 0 (4.2)
The most widely known example is the van def Waals equation 118731:
RT •
p'--.-"
v- .,
(4.3)

This work uncovered a field thaI has been lhe subjt'Cl of numerous studies thaI are still
ongoing. and into which we can provide but a glimpse. In 1983. R.C. Reid presented a sta-
tistic on the literalllrc devoted to tile topic and especially all the Redlich·Kwong equation
of slate (Table 4.1). and concluded; "/1 is (I full-lime jQb 1'''$/ IQ maimain (l fomiliaril)' ...ilh
the IICW I/cI·l'1opmeIllS in /his fi~ItJ··!

Table 4.1
R"rcrcn«:s f.t>.n Chemic,,1 AbslrtN:/S on equations of stal", IReid, 1983]

Period Equati<lns of Slale Redlich·Kwong EqU&lK>n


1982 ". ""
1980-1981
lm-l'fl9
1972-1976
1 III
"116
"" J9
J9
1967-1971 m
'"
There ill no doobl wlllltsoen, Ih,t Ihis interesl is rooled in Ihe abilily Cal 11'.,,;1 in prinri_
ple) of lhe equlions of slale 10 cakoJale alilhermod)'nlUnk propel1ies, iJt par1icul.. Ihe
pha§e equilibria.
Using the equalion of state. it is indeed JXlSSible. by applica,ion or Equations 1.44.1.45.
and 1.50 through 1.53.10 calculate the efreCI or volume or pressure variation on the lher-
modynamic propertics. Through integration (Eqs. 2.27 to 2.34). we can thcn calculate the
100

deviations from the ideal gas laws or residual quantities. For cltample. for enthalpy we
have:

h....(1'.P) '" 11(7,/') - h'(7.1·) .. f: [v - r(:; )J dP (2.27)

or. IJ,..(TJ') .. h(T.I')-h'(1',P)= f (T(~;)v -1')dV+I'V-RT (2.29)

If .....e also use the heal capacity in the standard stale. the value of Ihe thermodynamic
properl), may be calculated using:

/r(T,p)=IJ~(To)+fT c;dT+(h~h') (4.4)


'.
Conversely. an equation of slale may be developed from an expression relating one of
the residual vallies to Ihe conditions of temperature and volume (or pressure). The follow<
illg expression for residual Helmholtz energy:


II-a =-RTln
(,,_b) •
- - -- (4.5)
, "
yields lhe van der Wilals equlIlion by derivation wilh volume at eonstllnl temperature and
applying &julIlion 1.44:
dA=-SdT-PdV or da=-.fdT-Pdu (1.44)

This rdationship between equations of state and expressions of residual properties


must be stressed. Indeed. statistical thermodynamic ob$crvations generally yield the value
of the residual quantity usually related to Helmholtz energy through the partition func-
tion. from which the equation of state results.
Furthermore. this relationship is the key to phase equilibria calculations using equa-
tions of state. At this point. it is appropriate to explore one of the objections that may be
raised when applying equations of state to the calculation of thermodynamic functions in
the liquid phase. If we state that there is an equation of state capable of simultaneously
describing both the liquid and vapor Slates for a pure sub:slance. we see that in the pressure
volume diagram. II continuous isotherm trnce like the one in Figure 4.1 can be drawn. On
this isolherm we can identify:
• Curve A8 related to the vapor phase
• Point 8 representing this vapor at its dew poim
• Point C rt'presenting the liquid at ils bubble point. and
• Curve CD related to the liquid phase.
If the equation of state is well chosen, this line will filthe experimental data. However,
on the continuous line corresponding to the equation of state. we can also identify a curve
8M thaI we may relate to II metastable vapor state that OCCUTli laIc com~red to the
condensation phenomenon. and that is 10 a certain extent experimentally reproducible.
We also sec a cur.·e NC related 10 a liquid that is also metastable. Curve !tiN on the
other hand does not correspond to any physical reality because along this curve the
mechanic slability condition dPldu < 0 is nOI met.
101

,,---------------------,
D

~
:!. •
------c
j
, N

, '00

We can now have doubts concerning the validity of a residual function calculation in the
liquid phlll>e that uses an equation of slale since it will include an inlegralion step over an
unstable ~one rOT alilhermodynamic values. For example, ....e have:

gl'-8'"" 0
f'.. ( u- RT) dP
P
by applying Equation (2.30).
The vapor liquid equilibrium condition in particular is obtained by equation:
P'" .v.~
gV,"-81.."=
fP"'••J--
IldP=O (4.6)

which can be read in Figure 4.1 using the equal areas contained between isotherm P(II)
and the slraig.hl ordinate P". This condition is very important. We call it Maxwell'li condi-
tion. II is a ooncrele expres!iion of Ihe relationship lhal exist!l between the equation of state
and the vapor liquid equilibrium.
In faci. Ihe doubt surrounding the validity of an integration .....ithin an unstable range is
removed if e consider thaI the Ihermodynamic model has its origin in a Gibbs energy
model thaI e assume is valid for Ihe t.....o phases. Furthermore. in the absencc of any other
hypothesis. the C<juation of Slate thai results is obtained through a derivation thai docs nOI
include the unSlable region:

(4.7)
102

We can see that an equation of stale may ,'cry well represent the volumetric behavior
within stable zoncs. but yield poor results for the vapor pressure if the representation of
the unstable zone is insufficient. On the other hand. it may allow for good calculations of
vapor pressure but yield poor values for ,'olumc (such is the case for most two parameter
eubic equations that we shall enoounter later on).

Classification of Equations of Stale

It would be good to be able to formulate a simple classifICation for the equations of state,
It is even necessary. in that an account should be methodical. For this reason, we shall dis-
cuss in sequence the equations of Slate derived from the virial development. those derived
from the van der Waals theory, etc,. selecting the structure of the equation as our classifi-
cation criterion. The qualities that characlCrile this or that equation are of a variable
nuture. and it would be necessary to have each one of them corn'Spond to a parlicular clas-
sification.
Because the expressions that are oommonly used are imperfect and do not meet all
needs. it seems to us that the most important criterion is the nmge of IIpplication of the
equation in question:
• Whllt compounds. or whllt familit'll
• Whllt properties
• What flInge of pfftl>ure lind tem~flIture.
Hence. we shall. for example. auribute particular importance to the equations of state
devised to represent the liquid-vapor equilibria of non·polar compounds.
We shall also pay allention to the predictive charllcter of the equution of stale. most
often obtained by application of the corresponding states principle.
One criterion that may appear to be related (0 this predictive character is the number of
pllfllmeterll and. of COUrllC. their physiCllI signiliamce, This criterion assumcs a particular
importance when applied to mixltJfcs because most often wc must dcfinc a la\\' of compo-
sition for cach of these paramcters.
The mlllhenunini upreMion must be taken il1to account, We shall draw a distinction
between equations e~plicit for pressure or volume- We will consider its complexity, which.
upon resolution of the equation of state, may entail a lengthening of the computing time
that may be prohibitive. Above alL Ihis complexity rish introducing serious incongruities
at the limits of the application range of the equatiOfl of Slate. or in extrapolation.

4.1 EQUATIONS OF STATE DERIVED FROM


THE VI RIAL DEVElOPMENT

The value of the compressibility factor for a fluid may be de"c1opc:d as a series around the
point where real fluid and ideal gas merge, which corresponds to a density of zero.
103

ThUs. we have:
B C
Z~I+-+::1+'" (4.8)
" "
The coeffidents B. C. eiC. for pure substances are only a function of tcmpcnllure and
are called the second. lhird. CIC. viTial coefficients. We have already encountered the sec-
ond vinal coefficient in our study of the propcnics of real nuids.
If the funclion Z(T.lI) developed in this way is the unknown function exadl)' corre-
sponding to the experiment. the virial coefficients ....ill be regarded as defined physical
properties. They will be sUbject 10 experimental determinations. and compilations or them
exist. Example 4.1 gives an example of the treatment of such experimental results. We Iia,-c
also provided a correlation of second virial coefficients wilhin the scope of the correspon-
ding Slates principle (Chapler 3. Section 3.2.2.1).
On Ihe olher hand. if the function Z(T,I') is an equation of state. the corresponding
development also allows us to define the expressions for the virial cocfficienLS aswciated
with this equation. For examplc:

for 1I --t 00 (4.9)

Of cou~. applying thcse equations allo\\o'S us to find the experimental values of the vir-
ial coefficients only if the equation of state eOITCl:t1y represcnLS the nuid. ~amplC5 4.1 and
4.4 that follow illustrate these distinClions.
We can also define a devdopment for pressure:

Z=I+B'/'+C'P2+.,. (4.10)

"'hose parameters are related to the virial coefficients by equations-the first two of which
we shall COnsider.
, 8
8.- (4.11)
RT

(4.12)

These sequential developments arc not looked upon as an equation of state since they
have an infinite number of terms whose values Dre unknown and whose calculation is
impossible. Yet their truncation has given rise to the Mvirial equations or statc" that we
charaCleri1.e according to the degree of truncation and by the nature or the development
from which they are derived, whether volume or pressure. Certain equations of state result
from a combination of truncation and empiriealterms that assures them eXIl:nsive validity.
The best known is the Benedict. Webb. and Rubin equation of state.
104 4. fqwlionsolSldle

o EXAMPLE 4.1
Determination o( the second and third virial coefficients
(or ethane (rom experimental data
We shall consider a sel of "pressure. volLimc. temperalLlrc" data for ethane. and using
these data. we shall detennine the second and third virial coefficients at several tern·
peratures.
To accomplish this. the development .....ill be used as follows:
C D
(Z-I)v:B+-+::1+
, "
and for a given temperature. we will use the values of the product of (Z - I)v as a
function of the rdation I/l!. The limit of this prodLlCl for Ilv ~ 0 is equal to the second
virial coefficient 8. and the slope at the origin of the curve is eqLlalto the third virial
coefficient C. Table 4.2 shows the data for preSSLIre and molar volume at 25"C. and the
calculation intermediates.

TabkO
Determination of the IiC«lnd and third virial roefflCient$ for ethalW a1 25'C

p , Z Ilm, (Z-I)"
,,
(bar) (em'· moI-')
0.9925 0.0406 -185.7
10
"""
4767
2'"
0.9614
0.9205
0.2098
0.4382
-183.9
-181.4
0.8767 0.6902 -178.7
"
20
'«9
Ill'" 0.8291 0.9731
1.2987
-175.6
-172.1
"
311
770
592.2
".,
0.n66
0.7167
0.6445
1.6887
2.1908
-167.8
-162.3
"'" 337.4 0.5444 2.9642 -ISH
41.876
2'"'' 0.4846 3.4862 -147.8

Using Figure 4.2......e can detennine the values for IJ and Cat O. 20. and 25°C. The
results are listed in Table 4.3.

Table 4.J
Scrond and third ~irial coeffICients for ethane at 0.20. and ZS'C

T 8 c
'K1 (eml·mol-') (em O.moI- 1)
273.15 -223 11206
-1113 11 lOS
2'!I3.1S
"." -,.- 10970
•• fqwtions 01 Stiote '05

-,."
-,'"
- -, ..
>

"
-"'"
-=.v'---
o , , , •
""0"
Flpre 4.l Determination of ,,,., oerorKl and third virial roeff"lCienl of
ethane from uperimenlal dalD.

We note that despite the relatively extended pressure interval. the development of
the truneated virial after the third term is a good representation of the dala. with the
exception of the critical isotherm for which we observe appreciable deviations.

4.1.1 Volume Virial Equation of State Truncated after the Second Term

The simplest and most applied of II.lIlrunClilions is wrinen as:


_ 8
Z", I +- (4.13)
"
As can be expected in view of its simplicity. its application range is very limited. II takes
inlo account the Vllpor phase allow pressure only, and its precision decreases with increas-
ing pressure. In general, we slate thai il may be u5ed up to half the critical pressure.
This equation of stale is e~plicit for pres.~ure but of the second order for volume. and
only the root oorresponding to the vapor phase is to be retained. Note that with an itera-
tive calculation where pressure is unknown. it may happen that it has no real root. On a
diagram Z(P) analogous to those shown previously (Fig. 2.3 or 3.8). il is represented by the
parabolic equation:
RT RT
p= If Zl_ Ii Z
106

thaI passes through points P = O. Z '" I and P '" O. Z '" O. The former corresponds to the
ideal gas: the laller is extended well beyond the range of applie-.alian for the equation. This
parabola is tangemial to isotherm Z(P) at the P '" 0 and Z = I coordinah.'s,
The values for the second vinal coefficient that will be used when applying Ihis equation
of state may come from experimental data specific to the component investigated. However.
most often they lIrc predicted using a correlation such as the one thaI we introduced
(Chapler 3. Section 3.2.2.1) as a fundion of reduced coordinates and the acentric factor.
The e;t;prcssions for residual funClions at given temperature and pressure that corre-
spond to Ihis equation of state are simple. They are obtained ViD the previously described
procedure (Chapter 2. Section 2.4) as the equation is not explicit in volume. We lind:
d8
8-T-
dT
lJ.-.lUt(T.P) = II -IJ' = RT ---'''- (4.14)
"
d8
8-T-
_ _ ~d~TC
s,.,.;,JlUl(T.P) = s - s' = - R + R tn Z (4.15)
"
In If! = gre&idl>al(T.P) '" 28 -In Z (4.16)
NT "

4.1.2 Volume Virial Equation of State Truncated after the Third Term
8 C
The equation: Z =1+-+::1 (4.17)
" "
is lillie used. Indeed. the addition of a third term does not allow (or a representation of the
liquid and vapor states with acceptable precision. In particular. ""e note that the applica-
tion of the critical constraint (Eq. 2.4) yields a critical compressibility factor of 113. clearly
greater than the experimental values. Furthermore. the values of the third virial coefficient
are not well known. Finally. when ~pplying this equation of state to mixtures. a composi-
tional dependence law must be defined for this coefficient. Supposedly representative or
the inter~ctions between three molecules. its expression involves ternary parametef1l
whose estimation is empirical only.
More advanced developments ha\·c. however. been applied to naluralgas. They altow
for a very satisfactory predictive density calculation [Jacschke /'1 ul.• 1991 a. 1991 bl.

4.1.3 Pressure Virial Equation of State Truncated after the Second Term

'llIe simplest of allthesc equations is ""rinen as:


8P
Z=I+ (4.18)
RT
107

or: v"',,·+8 (4.19)


II is explicit for both pressure and volume. Note lhallhe use. 01 the ..-inal equalion 01
slate with pressure lnmcaloo after Ihe second term substitutes lhe iwtbemu 01 the rom-
prltSliibllity flldot' ..ilh the bundle 01 lines lhal is tangcnillol 10 them al points P. O. and
Z. I, and whO$C slope is equal to BINT. II is therefore easy to qualitatively estimate its
validit), range. II is temperalUre dependent a5 an examination of Ihe Z(P) diagram shows
(Fig. 2.3 or 3.8). Al low reduced temperatures, it is limited by the two-phase cnvelope. but
al higher reduced lemperalllres, il extends 10 very elevated pressures,lhe isotherms Z(P)
being practically linear. or C:OUrR. the equation can he 'PJtI~ 10 the l'IIpor plutse onl)',
The expression for residual function is espeeially simple:

hrniduoJ{T.P) ~ (8- T ~~) P (4.20)

g'nlo!uol(T.P) BP
1011': =0- (4.21)
RT RT
Even though this fonn of the virial equation of state yields results that are slightly less
precise than thO$C of expression (4.13). we prefer it for reasons of simplicity.

o EXAMPLE 4.2
Calculation of an isentropic compression
We shall calculate temperature variation as a function of pressure during the com·
pression of lI·butane, which is supposed adiabatic and reversible, and therefore isen-
tropic.. The pressure virial equation of stale Iruncated after the second term will be
used. The second virial coefficienl will be calculated using the simplified expression:

Heat capacity will be furnished by the equation:


cO"'a+bT

The CQrresponding numerical data arc:
a: 197.1 em)· mol- l p: 8.31.101 em J • mol- I . Kl
a'" 22.97 1 . mol- l . K- l b '" 24.91:1 . 10-1 1 . mol- l . K-1

The initial conditions arc: T: 278.15 K. P = I bar. and the final pressure equals 6 bar.
By applying Equation 1.53 thai expresses the variation of entropy with temperature
and pres.~ure:

dS:C,. dT ~('V) r
T oT
dP or ds=c,. dT _("") dP
T aT,.
(1.53)
108 4. fqwtioosoiSIdIt>

it is possible to derive the temperature as related (0 pressure along the isentropic:

T~),
(:~): (4.22)

The leons on the right hand side may be arrived at by applying the equation of slate.
[\ is recommended 10 usc the heal capacity at standard state c; (ideal gas) and the
residual term for the c<llculation of the heal capacity. In any event. we cannot inte-
grate the obtained differential equation.
II seems simpler 10 express the entropy using:
sf T,P} = SO( To-I"') + [sO{T.P") - soC Tll'P"1I
+ Is'( 7'/') - s"( T.P") I + [sf T,P) - s'( T(tP) I (4.23)

In this equation. we recognize successively:


• An arbitrary ~or;ginM value chosen for cntropy. at standard suite (ideal gas. pres-
sure of 1 bar. temperature T.J.
• The inclusion of the temperature, thereby Obtaining entropy as a function of tem-
perature. always at standard state.
• The calculalion for the variation of entropy of the ideal gas between standard pres-
sure and pressure I' (this calculation would not have occurred with enthalpy).
• llJe residual cntropy tcrm.
Applying the virial equation of state for pressure truncated after the second term,this
residual term is calculated as follows:

i1(,-,')) dP=- dB d8
d(s-s'h=-- ( aT /' - dP
dT
and henet: s-~=--I'
dT
(4.24)

and is therefore wrillcn as:


T c" I' dB
3'('(,1') = ,,"(TO''''') +
f
T.
"!"'dT-Rln
T po dT
P (4.25)

If we designate the initial conditions with T l and 1'1' during isentropic compression
the temperature and pressure arc then link.ed by the expression:
T c' P dB
s"(T(Io"") +
f ..J:... dT - R tn - - _ P
T. T ". dT

':S'(T(IoP")+f"'T; dT-Rln
r.
~~(:~)T.T, P, (4.26)

We vcrify that the pressures and tcmperatures To and po as well as the entropy under
these conditions $" (T(IopO) arc eliminated from this equation. To perform the calcula-
tions. and in particular to obtain the numerical value for the second mcmber. we shall
use the value SO (TO'P") -= 312.12 J . mol-I. K- l at 298 K provided by the elllropy tables.
Tak.ing into account the expressions that .....ere given fur the second virial coeffICient
and hClil capacity at standard Slate. we obtain:
110 4. fqu.>I;om of SI,lle

The condition may lherdore be expressed as:


rep " M"
R RT
The molar heal capacity for h)"drocarbons increases steadily wilh molecular weight
while the adimcnsional enthalpy of vaporization tU,"'RT varies little (Trouton law,
Chapter 2. l'~ble 2.7). From Ihis we can conclude lhal the lighler hydrocarbons
(methane, ethane) do not undergo condensation during isentropic compression
begun at the nonnal boiling tcmpertllun:: compared to compounds of higher molecu-
lar weight. The previous. more precise calculation shows lhal the limit is found to be
apprOJ;imalc1y at II-bulane.
We can finally compare the results of Table 4.4 ....ith the ones ....e obtain by comparing
II-butane vapor 10 an ideal gas. As we have ;uSI secn. for an isentropic change we may
,,'rile:
(4.29)

Applying this equation at a pressure of 6 bar. and neglecting the variation or heat
capacity with temperature. we find that T -= 332 K.

o EXAMPLE 4.3
Calculation of fugacity in the liquid and vapor phase
Considering Equation 4.21:

(4.21)

by applying Equation 1.53 that expresses the variation of entropy with temperature
and allows lIS to obtain a simple expression for the fugacity or a pure substance in the
saturated vapor phase:

r=fexp(:~) and r=p"ex p ('::;) (4.30)

We cannot apply the virial equation of state truncated after the second term to the
liquid phase. We shallthererore estimate the Po)'nting correction (Eq. 2.51):

tl.=!"exp [
"'"(p - I"')
RT
1 (4.31)

and ultimately:

tl.=P"exp 81"') exV ["'(P-I"')]


(Ri RT (4.32)

These calculations will be applied to the calculation of the liquid-vapor equilibrium


oocfficients.
4. (qwtions of SMe 111

4.1.4 The Benedict, Webb, and Rubin Equation 119401

This equation of state has been generally used to aHow the interpolation or smoothening
of experimental results that described the volumetric behavior of light hydrocarbons. If we
designate by p the ~molar density~. which is the opposite of the molar volume. p '" 111l. it is
written as:

p", RTp+ (BoRT -A a- ~ )pl + (bRT _U)pl + oap6


Cp'
... Tf (I + )pl) exp (_)pl) (4.33)

In theory. this equation may be applied to vapor and liquid state!, and to the cakul;,tion
of residual thermodynamic properties (enthalpy. entropy. fugacity coefl'icient).
As we see. it can be considered a development of the compressibility factor limited to
the second order as the additional term is empirical. At II given temperature. it has five
parameters., and in order to take into account their dependence on temperature. II total of
eight parameters. The values proposed for these parameters are generally specific to the
compound being examined. They may vary according to the range or the properly that is
under investigation. It was also formulated using reduced coordinates SO that the parame·
ters depend only on the critical coordinates. or possibly on the acentric factor. Here we
show the form proposed by Starling [1971. 19721:

Co Do Eo)
Z"'[+ ( 8 aRT-A o-TI+TJ--r P

(4.34)

where p~ denotes the critical molar density and wthe acentric factor:

(435)

We have also come across the formula used by Lee and Kesler (Eq. 3.25) to show the
properties of a simple fluid (methane) and of a reference fluid. We will have a chance to
cite more recent modifications regarding equations of state that are specific for cenain
pure substances.
Ir the precision obtained i~ generally mudJ srealer Ihan Iha' oblabted "'ilh equations
derhed rrom the ...n der W.als theory. it must be mllintllined that the IlIrge numb<rT of
112

pllnlmelen lind their IIICk ofph"siaLllipificance undermine tbe definition oroomposidon


rule!llUld. bec8u'Ie orlhb (m.lheir application 10 mixtures.

4.2 EQUATIONS OF STATE DERIVED FROM


THE VAN DER WAALS THEORY

We fecallthc equation of state proposed by van dcr Waals:


RT •
p. - (4J)
v--b - v'
-

Firstly. we T'ttogniu a repulsion term thaltokcs into account the volume of the molecules
using parameter h. or covolume. and secondly an attraction term. or internal pressure thai
is dependent on the parameter •.
The values for these parameters are determined by applying ~crilical constraints", and
at Ihis time we can elaborate on the consequences of such a choice. 1'l1ere are three
cOllslrainl.S. The equation of Slate is satisfied al the critical po;nl. as arc the equations.:

forT=T,andP=P, (2.4)

Therdore. in the ease of the van dcr Waals equation of state. we will have:
RT •
P~---::!
~ vc-b V c

aP) RTc 2.
(3v T=-(vc-bf+~=O
il'P) _ 2RTc 6._
( av 2 T - (v< b)j - v~ - 0

These three equations relate five quantities: the critical points T c ' p~ and v c ' and the two
parametcN of tbe equation of state. and b. We are therefore unable a priori to fix the
three critical coordinates. Generally. we choose to use the two parameleN of the equation
of state and the critical volume (or the critical compressibility factor) as a function of the
critical temperature and the critical pressure that are more widely known. For this reason
and for the two parameter equations of state. the critical points corresponding til the equa-
lion of Slate will not coincide with the experimental values except for the valUe!! of pres-
sure and temperature. with volume (or compressibility factor) being mostly overevaluated.
We end up with the equations:

(4.36)

RT<
b=Q~­ (4.37)
p<
113

The numerical values for ltle adimcnsional parameters n. and ~. and the critical com-
pressibility factor are:
27
n·=64' nb " , -I and (4.38)
8
If we lake: parameters II and b independent of temperature, all of the iSOIhcrms
obtained have the shape required. at least qualitatively, for describing liquid and vaPQT
states (lhe subcritical [salhem has a maximum and a minimum). or thc "supcrcrilical"
state (the isotherm is monotone). Furthcnnore, laking into account the two previous equa·
tions. we can clrpress the van def Waals equation using reduced coordinates:
Z I
Z= - n. ----:rr (4.39)
Z-D P, ZT.
h T, P,
This equation dl..~bcs the variation of the compressibility factor with reduced pres-
sure and reduced temperature, and exhibits the oorresponding slales principle as a conse-
quence of the van dcr Waals equation of state. This is how the law was introduced initially.
We need to emphasize the essential qualilies for what was the work of a pioneer: the
representalion for the different nuid states, and the prediction of lhe corresponding Slates
principle. We must also nOle the simplicity of the expression. At a given temperature and
pressure. lhe expression is lhird degree for volume and may be resolved easily withoutlhe
need for an iterative process.Additionally, the roots corresponding to the liquid and vapor
phases are easily identifiable. The equalions of state derived from the van der Waals equa·
tion are oflen called "cubic C<!ualions of stale".
Yel.as van dcrWaals himself remarked. this equation ofstatc is ofunacceptablc pn><:ision.
The compressibility factor that corresponds to it has a value (318) thaI is too high. and the cal·
culation of molar volume ill the liquid phase results til ullacceptable systematic errors in
exccss.ln addition. if we determine the vapor pressure by applying the MlUWClI condilion of
equalily of areas oonlained between isotherms p(1I) and isobar P".lhe results are erroneous.
These facts in part explain the considerable amounl of work lhat has continued lhe sludiesof
van der Waals.and thaI has led to the equations of state lhat are today oommonly applied.

4.2.1 The Soave-Redlich-Kwong and Peng-Robinson Equations of State

With the goal of better represcnting the volumetric properties of nuids, Redlich and
Kwoag 11949] proposed an empirical modification 10 lhe van der Waals attraction tenn.
They also introduced a temperature dependence for lhe parameter •.The Redlich.Kwong
equation of slate in its initial form is:
RT •
p. -.---. - CV1"T~.(~.-'~'~) (4.40)

where covolume b is related 10 the critical points by Equation (4.37), and lhe attraction
parameter is expressed as a function of these same coordinates by lhe expression:
I 14

(4.41)

For our purposes. we prefer to write the cquation of state in the form:
RT a{ T)
l' = -,,-_-. - :"i.(,~.~.,,) (4.42)

R 2T 1
with: a(T) = f}" T, a(T.) (4.43)

I
a(T,)"' ff (4.44)
,
and. as with the van der Waals equation:
NT,
b=f}b - (437)
P,
By applying the critical constraints, we deteonine the values of the parameters f}. and
q,. and of the critical compressibility faclOr. We find thaI:
I
f}. =
9(
2 1/3
- I)
... 0.42748 ,"d z, = ~3 (4.45)

The results as they conet:m the calculation of density arc definitely imprm·ed. especially
for the vapor phase. but remain mediocre for vapor pressure. The Redlich·Kwong equa·
tion of state. howe vcr. has pro"cd one of thc most useful. In particular, it embodies one of
the compon('nts of the method proposed by Chao and Suder [19611 for the calculation of
liquid vapor equilibria.
The hl"O-plll'lImeter rubic equations of slate are in fllCt unable to ",pl'e!i('nt bolh mlu.
melric: Mhavior and "lIpor pres.~ures with an lItteplabk- pl't'C'ision IAbbott.I989J. and it is
appropriate to determine a priority. This was undel'1ltood by Soa"e 119721 who applied the
Redlich·Kwong equation of state to the calculation of hydrocarbon vapor pressures.
Considering that the eoyolulllC retains the value corresponding to the critical point
(Eq. 4,37). it is possible to determine the value of the allraction parameter II at any tern·
peratul't' from the corresponding vapor pressure data (T.P"). by applying the equation of
state to the liquid and vapor phases and including the equilibrium condition (fugacity
equality). To fit the values thus obtained. Soave proposed applying the following expres-
StOn:
a(T,)=(l + ",(I-V1';W (4.46)

111c paramcH:r It! is specific for the component in question but its value was correlated
as a function of the acentric factor:
(4.47)

with: (4.48)
1

n[

p=

• 1Ul. ..
,. I

Pi
·D lim th

n .. nt

atJi n
116

Calculation ofThermodynamic Properties

By applying equations 2.29. 2.31 102.33. and 2.40. il ;s possible 10 calculate the residual
properties, in olher words the differences between the value of a thermodynamic property
for a Ouid 10 which we apply one of the simple cubic equations of slate. and the value cor-
responding to the ideal gas under the same conditions of temperature and pressure, As the
equation of stale is specific for pressure but not volume. the method illlroduced in
Chapter 2. Section 2.4 is l,J.."Cd. We shall do so for the emhalp)' and the fugacity coefficient
with respectlo the general cubic equation;
RT •
P = v---b - (C'C:;b",;,~):'(.:,C_'bC,,,,) (4.50)

which. depending on the value of parameters'l and'2 reprcscnllhe equations of stale of


van der Waals ('1 = '2 = 0). Soave-Redlich-Kwong (rl '" 0"2'" -1). or Peng-Robinson
('I':-1-0.r2",-1 + 0).

Calculalion of the Residual Enlhalpy


First. we will calculate lhe residual inlemal energy atlhe given temperature and volume:

u~I(T.II) '" !I(T.P.II) -11.( T.P· '" R"T. II ) : [ [T( ~; t-p] dll (2.28)

i.e.. by using general formula (4.50):

( d'lI"
II(T.II)-,j·(T.II): a-T dT ~
d,
(lI-b'l) (.1- b'2)
(4.51)

d•
• -T-
u(T.II)-II'(T.v) I dT
yielding: b U(,I.b.rI"'z) (4.52)
RT '" RT
where function U(IIJ)JIJV depends on the equation of state considered (Table 4.6). Since
the internal energy of the ideal gas is independent of volume.(or pre.-.sure). its residual value
at a given temperature and pressure is the same. For the residual enthalpy we have therefore:
d•
• -T-
h(T.P)-h·(T.P)
RT
.-I
RT
b
dT
U(II.b·'I·'Z) + Z - I (4.53)

If we use a temperature that is less than the criticaltcmperalUre and a pressure equal to
the vapor pressure (itself calculated using the equation of state). the application of this
equation to the saturated vapor phase (value of the volume corresponding to the largest
root of the equation of state). and lhen to the saturated liquid (value of the volume corre-
sponding to the smallest root) gives us the residual enthalpy of the two phases. Their differ-
ence is the enthalpy of vaporiultion.ln genera1.such an approach yields acceptable resull.s.
Note that the residual enthalpy expression uses the derivative of the allraetion parame-
ter I as related to temperature. If we were to calculate residual heat capacity. the seCQnd
derivative would be used IS well. Comparison of the results of such calculations is a mcans
4. Eqwtioros 01 Sldte 117

of validating the proposed 1(7) equations [Trebble and Bishnoi. 19871. The one proposed
by Soave (Eq. 4.46) yields satisfactory resul15 (Fig. 4.3).

-• "'"
,
, 300
~
~

~
"'"
".-

Figure (.) Heal capacity ()f elhane at roMtant prclo5ure (P • 6 MPa);


cakulalil)fl using lhe Soave·Redlich·Kwong e<juation of stale ( - )
and npcrimcnlal data (l!.).

Fugacity Coefficient

First we will calculate the residual Helmlloltz energy for a given lemperalure and volume:

urr.O,l..t(T.v) =a (T.P.v) _ a'( T.P' = RvT.v ) = 1: [- P + :T] dv (2.31)

I.e.: .
a(T.v) - a (T.v) "" f' (
..
- -RT
- + -RT +
v-b v

(v-b'J(v brJ
) d. (4.54)

a(T.v)-Q"(T.v} I (v-b) • ( ,)
yielding:
RT - - " - -
vbRT+ - - U v"",
...· ·
(4.55)

where tile function U(v.b"t.rJ is the same as lhe one used for the residual enthalpy
(Thble 4.6).
To obtain lhe residual Gibbs energy at given temperature and pressure. we proceed as
discussed in Chapter 2. Se<:tion 2.4.2 lind thus obtain:

g(T.P)-g'(T.P) p(v-b) •
RT = -In RT + Z -I + bRT U(v.b.r,.rJ (4.56)
1 quati

II

ll.l~-IJ, ~-~ . . -1 . ~rl ,.


II ,....

i . hi b
tEl

17.,
7 -41. ~-:-
L' II .' 7
- ••


. .In

I _......... 'Fr
to . '. U II 'n

I' l thr

rial
..
I
1

.
~ILJlI'UI'1ill,:IIi.'llll"'- n 0'

.D_
r-

··u .1

1'1~
'or -

.1 L

u f' iOI'''''!Q,'..·'. .. .,

- - .
1 ]

c~~nlcte:nt

'Ill
J~"" ... ,,,"'.l .

R'

if T,.,.

7.

R"

h It
,I'

'rmU~ i :I'::~. eo
.

=1. 1'- - --

tl'
~:t 1'JIl'.DII!'A

I' - th

7, ,1
,I

u
121

,,-,--;----------,

0------------------
~
,
~ -10-

,I
• ~20~

o 200 400 600


Molar YOIum8 lema. mol-')

Figure;l.4 Roots for Ihe Soave.Redlich·K....oog equation of Slate at


U'm pressuI"C. Application to benzene allll'f'C.

LJ EXAMPLE 4.6
Applicalion of the So.we method to the van der Waals equation of stale
We shall take here a "cry detailed look 3l lhe prOCCSli used by Soave 10 identify the
parameters for an equation ofstate.1lte numerical application relatcs to bcn7.enc 81 25"C.
Applying the van def Waals equation of state, we shall first determine the parameters
at the critical temperature. To do this. we use the crilical conditions or, more simply.
write the equation of state, as a third order equalion in volume:

II
,(NT
- p+b) I)
2 II lib
+pV-p"'O (4.63)

Allhe critical point, the equation has a triple rOlli, and is therefore equivalent to the
equation;
(11-"0)':0
We thus obtain three equatioos relating the critical coordinates to the parameters:
NT, (
3v,=- I+D.)
P,
now we perform the following transformation of variables:
2
II"''''' R T; b=D. RT< IJ =Z RTc
" p, P, " p,
where n.
arId f4, arc numbers with no dimension. The relationships between tile
parameters and the critical coordinate!! become;
32<= I +n~ 3Z;",n,. z;=f1.n,
The Mllutions for this system are:
27 I. 3
0."'64 ~=8 Z<=8
Allhc crilicallcmpcrature. and for benzene (T. '" 562.1 K. p." 49.04 bar), the values
for the variables are therefore:
11= 1.8817 J . ml. mol-1 b = 1.1929 10'" m3 . rnot- l
Ne~l we shall consider parameter b as independent of temperature lind we shall cal-
culate parameter II such lhal al 25"C the experimemal value of vapor pressure.
12.692 kPa (see Table 2.6) is exactly CIllculated by the equation of Stale.
If we designate .;.... and vl'AJ as the roots of the equation of Slale at equilibrium of the
liquid and vapor phases. and designate po as lhe vapor pressure, the following equa~
tions must be verified:
• (4.64)

po = RT • ("')
"V."_b ( 1I V.")! .
They represclltlhc application of lhe equation of Slate to the liquid phase and to the
"apor phase. The fugacity coefficients of these two phases must also be equal. For the
van der Waals equalion of state. the expression for this ooefficient is (Table 4.6):
P(lI-b) • b
InqJ=-ln +Z-I---- (4.66)
RT bRT II
and therefore we have:
f"'(IIL."_b) • b
-In +ZL."_I ~
RT bRT II .....
P"(IIV."~b) • b
=-In +ZI("-I---= (4.67)
RT bRT " ...
The three preceding equations allow for the determination of lhe three unknowns: •.
I,'·... and ,,1(... To simplify the problem. we take into account the fact that pressure is
low and. therefore. the fugacity coefficient is very close to unity since the Slliurated
vapor may be compared to an ideal gas. This simplification allows us to restricl the
problem to the liquid phase and relain only the equations:


-I , -

][ll'bile - 7

,n

i": L

-.
BOj~\fmion ~'fl'lraa~ons
I
S
-.
124

sity at satur3lion, the Rackell method is preferred (Eq. 3.14). Finally. for a pure substance.
if we are interested in all thermodynamic properties. the Lee and Kesler method yields
bettcr re5ulls. WhIten', tllt' case. the cubk equations of Shill' thaI ..'e ha"c just discussed
prndell' unly II medw.:re represenlilliun of lhe critinll ",gion. as shown in Figure 4.5 that
allows for a comparison of cxperimclllal data with the calculation of the critical isotherm
IlCbie\'cd by using the Soave.Redlich.Kwong and Peng-Robinson equations of Slate.
II is therefore for liquid \'1Ipor etjuilibria of mixtu~ under pre!iSure lhal the Soll,"e-
R«llidl·t\"'ong and Pcng·Robin.wn t'qllations nhlll1e lind their principlllllpplicalion.lmd
seem !lIthe pl"eSenl limt' 10 be ilTlCplll",llhle. We shall return (Chapler 8) to these methods
by defining "mixing rules" that link the values of the parameters with the composition and
upon which the practical value of an equation of state strongly depends.

4.2.2 Recent Developments of Cubic Equations of State

The generalif.cd <lpplicatioo of the Soave.Redlich.Kwong equation of state to calculations


in chemical engineering and to the exploit"tion of petroleum nuids (natural gas.. crude
oils) has given rise to a large amount of work aimed at rectifying the shortcomings.
Limiting ourselves in this chaptcr to the formulation of these equations for pure sub-
stances. which is only a first but essential step. these naws lie within predictions that are
sumetimes inadequate for vapor pressures. and generally mediocre for volume. Without
trying to provide an e~haustive account of modifications that ha\'e Ocen proposed. we will
prcsclll a few examples.

'" ,
,,- It.,'
,,,
.. 20- ,,,
,• 4
,,

•O 'S-
, ,
£ ,,-
,< .'
,

,- "'''''''''~'''''''~~''''''',ii',•
"

0
, • 8 to 12
0 4
Molar deosity (mol' 1-')
" " '"
f1Bur., 4.5 Cakutation of the crilical isotherm for ethnne: using
the Soave·Redlich-Kwong ( - - ) and the Peng·Robinson (- --)
equalion~ of Slal~. Comparison 10 experimenlal dala ( l>.).

" j
4. f"u•• rionsol5Mc 125

4.2.2.1 Dependence of Attraction Parameter 'a' on Temperature


It may be essential 10 precisely reproduce the vapor pre~ures for the components of a
mixture. Such is the case with He." (butane. isobulane. and butenes) hydrocarbon fraelion-
alion sludies where relalive volatilities are dose to unily. In this ease. the selection of an
appropriate -(n equation is more important than the moire of an improved mixing rule.
It is equally important to make use of precise expressiOnli when studying and comparing
the mixing rules who:se effects may be masked by an inadequacy of the a(n law.
If for such components we have acres..~ to accurate experiment/ll vapor pressure dala. or
a satisfactory fX'(n expn:ssiOIl. it is then possible to match an anraction parameter value
to each point on the experimental vapor pressure curve. We may then correlate the results
obtained in the form of an a(n law lhat is more accurate than the one proposed by Soave.
but specific to each component. The main problems concero the extrapolation of this law
to temperatures that are higher than lhe critical temperature. or to low temperatures, and
its possible generalization for predicting its parameters as was done for Equation 4.47
using the acentric factor.
Extrapolation beyond the critical point requires particular attention. If we adopt two
distinct expressions according to the temperature range. one must be aware that the calcu-
lations for enthalpy will undergo discontinuity if the derivative daidT is not continuous. It
will be the $ame fl)l" heat capacilY if the second derivative is not also continuous.
Furthermore. in the supercritical region we cannot rely on volumelric data that are poorly
represented by these equations. Ho....ever. we must note that this difficulty occurs only in
cascs of compounds for which the range of study includes the critical temperature. which
limits their numbcr.
As for extrapolation to low temperatures. we are faced ....ith a scarcity of experimental
data that allows for the estimation of the quality of the proposed correlation.
Among the numerous expressions that have been proposed, we quote some examples.
Mathias and Copeman 11983] apply the following equation to the Peng-Robinson equa-
tion of state:
(4.68)

which is the $arne as the original equation if parameters c: and c] equal zero. II is in thi!
way that it i! applied for the supercritical region. The values of the three parameteT!l are
specific for the substance being studied. and there is no allempl to generalize them. Of
course. this uprcssion may be applied to either the Soave-Redlkh·Kwong equation or the
van der Waals equation as long as the numerical values of the parameters differ.
While preserving the general expression for the attraction term:
RlTl
a(T) .. n .. T a(T,) (4.43)

Stryjek and Vera lI986] proposed an expression for lhe IX parameter as a function of
reduced temperature:
(4.69)

where the parameter "'0 is calculated from the acentric factor. and the parameter"" is
adjusted using the experimental data lsee Proust and Vera. 19891. In the supercritil;lll
". •. Equd/ions of SMe

domain,lII j is considered zero. Its application to the calculation of vapor pressures for a
large number of polar and nonpolar compounds yields good Tesulls. II is. however. impor-
I:mllhlllthe values for the critical coordinates and the accmric factor are idcnlicallo those
used by the authors.
When the only modifications introduced to the equation of Siale relate to the modifica-
tion of the law linking the attraction paramcler to tempemlure. the consequences for the
calculation of the volume arc minimal. or course. it is not the same if the attrncl;on term is
modifted.ll1e examples thai we shall provide now have both a more profound modifiea-
tiOll. and often the suggestion of a new IItn law.

4.2.2.2 Modifications of the Attraclion Term


Applying the critical constraints 10 an equation of state having only two parameters alloll.'S
only to comply with two of the eKperimental critical coordinates. and the critical com-
pressibility (actor is determined by the fonn of the equation. generally lln underestimation.
The usc of a third parameter provides an additional flexibility if we wish to estimate liquid
vapor equilibrium and volume at the same time.
Schmidt and Wenzel 11980). Harmens and Knapp II980J. Heyen II980J. and Patel and
Teja 11982) suggest an equation or state that corroborates the general equation:
RT •
P= ;::t; - vI + lIbv + ",b1 where II + ... = I (4.70)

The fundamental inadequacy of equlltions of state to correctly represent the critical


lone and the saturated liquid at the same time mak.es it impossible to choose a third
parameter such that the three critical coordinates are exactly dl.'SCribed. Although the
methods chosen by the authors ror the calculation of the paramcters differ. the resuilli are
not fundamentally dirferen!. The mOSt applied of these equations is undoubtedly that of
Patel and Teja. which has the rorm:
RT •
p~ - - (4.71)
v-b v(v+b)+c{v-b)
As we noted above. the critical compressibility factor. '" imposed on the eqllation of
suite differs from the experimental value. It is related to the acentric factor by the equa-
tion:
'" = 0.329032 - 0.076 799w + 0.021 19-17w~ (4.n)
This equation of state is similar to that of Redlich-Kwong for simple fluids (w= 0) and
to that of Peng-Robinson when the acentric factor is in the neighborhood of 0.3. Ii pro-
vides a llscful compromisc belween the two equations.
Through the critical condition intermediary. the other parameters dcpend on (.. We
apply the usual equations:
(4.43)

(4.37)
4. Equar......,ciStotre 127

RT,
e:=£2" - (4.73)
P,
n.. i~ the smal1e~t positive root of the equation:

(4.74)

n. and n. are calculated using the equations:


n. ~J'1+ J(I-2(Jn..+ n~+ l-JC", (4.75)

(4.76)
The variation of the anraetion parameter wilh temperature is monitored by an equation
that is identical to the one proposed by Soave:
aCT,) '" [I + /11(1 - v'T.>F (4A6)

where the parameter /II is related to the acentric factor (for apolar substances):
m '" 0.45241J + 1.J0982Ctl-0.2959J7ro1 (4.77)

Thc results obtained using this method arc analogous to those produced by the method
proposed by Schmidt and Wenzel. They are improved. particularly for the calculation of
volumes when compared to the two parameter equations. The coneept of translation will
allow us to investigate this improvement. It remains understood that the behavior in the
critical zone remains poor.
l11e equation of state proposed by Heyen distinguishes itself by the fact that covol-
ume b varies with temperature. Thus it is possible to represent molar volumes for saturated
liquid with good precision. However. Trebble and Bishnoi [1987] have recently shown that
such a variation may cause incoherences for the calculation of heat capacity.

Volume Translation and the "General Cubic Equation"


We can in fact recover the various equations that we just cited using the "volume transla·
tion" concept. introduced by Martin [1979]. and whose value was shown by P~neloux 1':/ 0/.
(1982].
If we suppose that we are using two equations of state e(T.P.v) .. 0 and e'(T,P.I/) '" 0
such that at a given temperature and for all values of pressure they provide the values"
and v' for the volume. differing only by a constant value e(v. v' -e), that (possibly) only
depends on temperature. their graphical representation of volume versus pressuTC
(fig.4.6) is made up of two curves. one translated from the other. If at a certain pressure P
the Maxwell condition (equality of areas located between curve p(v) and isobar P) is
respected for one. it is also respected for the other. These two equatiolili of state therefore
yield the same results for the calculation of vapor pressuTC. Hence the calculation of vol-
umes and phase equilibria are to a certain extent independent. This method is. of COUl1iC,
valid for any equation of state, but ;s especially effective in affording otherwise lacking
nexibility to the methods derived from the van der Waals theory.
128 •. fqua/ions 01 Si~/t'

5 -,----,,---------------,

.'

, , ,
o '00
"" 300 <00

"rliese equations are listed according to Ihe general formula:


po RT _ •
(4.78)
p'-b' v'[II'+yb'l
"",v'-(: (4.79)
b;b'-c (4.80)
The firsl equation is lhe "generalized cubic cqu3lion" Ihal yields.. via translation
(parameter c). the equation:
NT II
---
,,- b (v -+- ()Iv -+- c + y(1l t e)l
(4.81)

Like equations 4.50and 4.70. this equation may be representative of alilhe "cubic" equa-
tions thai \\'1,' have previously encountered. We establish IIII,' following correspondences:
Redlich-Kwong Equation: y= 1 and c '" 0
(4.82)
2
Peng-Robinson Equation: y= ~ lind c = -b(V2 - I)
v2 - 1
All the equl11ions of slale stemming from lhe general e~pression 4.50 lhal. for e~ample.
correspond to this lasl value of y. and for which parameter II is calculated according Lo the
equations recommended by Peng and Robinson. will yield the same results for the liquid-
vapor equilibrium calculation. Yel lhe calculation of molar volume will depend on the
v11lue of c.1'his value may be adjusted for the substance in question. Indeed. we frequently
use dala such as density al ordinary temperature or. for low molecular weighl compounds.
4. fqwt~afSlare "9

the normal boiling temperature. We may then calculate parameter e such that the equation
of state rcturns uactly such data. It has al!;Q been proposed Lhat e be correlated as a func-
tion of the RadclI factor.
Translation of the van dcr Waals. Redlich-Kwong. and Peng-Robin!;Qn equations has the
eUect of evening out the considerable differences Lhey produced in the calculation of
molar volume.
The translation ternl may vary with tcmpcralllre. and we may be tempted tosubject it to
a law such thalliquid volume is restored along the SlIturiltion CUI'Ve. It results in a rapid
variation of its value around the critical point that cannot be extrapolated within the criti·
cal region. In addition. neither the critical isotherm nor the i!;Qtherms in the critical zone
are really improved because the translation docs not correct ror the shoncomings of the
cubic equations within this region.
The diUcrences between tile thermodynamic properties of the liquid and vapor phases
in equilibrium are obviously not modified by translation. Thererore-the enthalpy of vapor-
i:t.ation remains unchanged.

o EXAMPLE 4.7
Application of the translation to the van der Waals equalion
Returning to the previous example. "·e will determine the translation paramder roc
benzene such thotthe molar volume in Ille liquid phase at ZS"C i!I represented exactly.
The experimental value is available in the literalllre: 88.3 em J · mol-I. We furthermore
ca1culated the value thai corresponds to the van der Waals volume (135.4 cm J • mol-I)
where the. parameter is determined such that at the given temperature. the vapor
pressure is corredly described. The translation that must be performed is therefore
equal to tile difference between these two values. or 135.4 - 88.3 '" 47.1 cm J . mol-I.
After application of equations 4.79 and 4.80. the newly derived equation of state may
be wrilten as:
NT •
p", lJ~b - (11+0:)2 (4.83)

The value or parameter. is unchanged. but parameter b undergoes translation lind.


laking into account the previously determined value (119.29 cm l . mol-I). becomes
equal to 72.19 cm l . mol-I.
We ~llnb:e the C1aWiht:'l equal",n or slllie in the preredinll equatinn.

The SBR Equation of State


Whatever Ihe modifications 10 the van der Waals equaLion of stale. il seems impossible to
satisractorily reprcsenlthe ··crilical region This shortcoming is 10 a certain extent com-
H

mon to any analytical representlltion of this region. II is particularly striking in tile case of
equations thol are as simple as the ones we hove dealt with up until this point. We can try
130 ~. f'l"dliom <Ii Sl.lte

to remedy this by abandoning Ihe cubic structure of the equation of Slale. It is in this way
thai Behar 1:1 al. [19851 proposed to "develop" the al1ractiOll term of the Redlich·Kwong
equation using density:

"=---
HT
v-b

lI(v+b)
b (b)']
[ l-r-+o-
II Ii
(4.84)

"l'llc four parameters of this equation vary with temperature. Their value has been roT-
related as a function of reduced temperature and the acentric factor. In order to beuer
represent the vapor pressure of compounds wilh high molar mass. their fonnulation has
been revised recenlly !Jullian l'/ al.. 19891.
The critical constraint has not been included in the determination of the parameters.
Ncverllleless. because of Ille close attention paid to the volumetric bcha\'ior in Ihe critical
region. the calculated critical points are reasonably close 10 the experimenlal data.
This equation marks undeniable progress in the calculation of volumes as a function of
pressure and temperalure in the critkal7.one and for the liquid phase. It yields results anal-
ogous to those obtained when applying the Soave or Peng-Robinson methods for the esti-
mation of vapor pressures.. The fact that due to its structure its resolution demands an iter·
ative calculation should nol be considered a serious handicap. It has been applied to the
calculation of phase equilibria for petroleum mixtures (crude oil and natural gases).
However. it applies only 10 non-polar compounds.
We can compare this equalion to the one proposed by SUluki and Sue [19891 thaI has a
similar structure. and has been applied 10 alcohols.. ammonia. and water on the condition
IhM specific parameters are used. Results have been generally acceptable.
[I is not pertinent 10 list here the innumerable variations of lhe van der Wal,is equation
of state thaI have been proposed. They embody a fair amount of empiricism. and the
acceptable results that have been obtained are in fact due to a fortunate balance between
the inaccuracies contained within the expression for the repulsion term. and the various
forms thaI ha\'c been proposed for the allraction term.

4.2.2.3 Applicalion of the Concept of Group Contribution


It is difficult to apply Ihe equations that we have jusl described to hydrocarbons of high
molecular weight. Indeed. their paramelers are calculated using critical points and these
points are nOI always known or cannot be determined experimentally due to heat decom-
position.1t is certainly possible to apply one of the numerous structure property equations
proposed for these parameters (Chapter 3). but we are aware of their faults.especially with
respeclto extrapolation. Furthermore. Ihe equation of state will be applied more often
wilhin a range of temperatures lhat are much lower than the Crilicaltemperature. and the
application of the usual equalions to the calculation of these parameters necessitales a
cumbersome delour. Finally. we note that the application of the corresponding Stales prin-
ciple to high molecular weight Struclures is a poorly justified eXlension of it.
It has therefore been proposed that we apply the methods of group conlribution to the
equation of slatc parametcrs. We recall the example [Coniglio. 1991: Coniglio er ul.• 19931
of the general cubic equation 4.78 where r is fixed at the value corresponding to the Peng-
Robinson equation of state (see Eq. 4.82).

p'
4. fquariQtlSofSwe 13\

The parameters to be determined are therefore eovolume b. the attraction parameter ...
and lhe translation tenn e-
We consider that the covolume band lhe Viln der Waals volume V", are proportional:
V.
b '" b(CH~) V.,(CH.) (4.85)

where the V:1n der Waals \'olumc is calculated using:


, ,
V~, '" L NIV•.,j + L
I_I ~-I
1~6",,~ (4.86)

in whieh Nj represents the number of groups of type j. V"\J is the contribution allributed to
them. 6.... IS the corrective term that corresponds to strueture k. alld I~ is the number of k
struetures present. The groups in question correspond to the simplest hydrocarbon struc-
tures (Table 4,8). and in order to take into account the ring structures.. we introduced the
tenn t\:~.

Table oUI
Group ronlribution~ and structural increments for tbe estimation of
van der Waals volume (Eq, 4.86) and translation votume (Eqs. 4.96 and 4.97)

v. ,
Groups
(cm 3InlOl) (cml/mol)
Alkanes
Cli) 13.67 30.29-10
Cli z 10.23 11.9370
CH 6.78 -8.2039
OualemaryC 3.33 -211.0458
Aromatic group'
CH
Substituled C .'"
,,.. 16.7162
-2.8986
Cundcn""d C ring 4.74 7.1473

Napluhenk rinl
Structures
'.
-1.14
'.
35.5932
Cydopentyl or eydohex)'1
Free or CQlJdensc:d.lrarrs
(IMtls-de<;aline)

Naphthuk rinl -2.50 37.3768


Cyclopentl'l or eyclohexyl
F«.'C or rondenSl.'d. cis (ci.<-<Iecaline)
Melh)'1 ring -1.66 37.9048
Condensed at bcnll't>C
(tetraline. indane. etc.)
132

The calculation for the annelion parameter is based on the following equation:

(4.87)

where II (Tb) is the value that corresponds to boiling temperature 0\ atmospheric pressure.
Functions 'I(m) and!l(m) are dependent on a form parameter /II:

1(11I)= C,
[ (XG-Y)
] m- [C,y] (4.88)
I (.tez-y)

lim) = [(XC~- y)] m - [(X~~ xy)] (4.89)

wilh C 1 '" 12.5295 and c; '" 41.389I ..r '" 0.05. and y '" I.
Thc form parameter m is calculated from lerm S. which is itself arrived al by group con-
tributions:
Ill'"

S=
,
L N,Mj + L 'tan t
.
0.34190 +5 + O.I8413S l (4.90)

(4.91)
/k\ t~l

where NI is the number of type j groups. Mj is the contribution auributed to them. !itllt is
the corrective term corresponding 10 structure k. and II the number of k structures
involved. The groups under examination are the same lI$ those Ihal relate 10 the calcula-
tion of the covolumc. but the Slructural effccts are different and take into account the
effects of chain length. substilUtion. non·planar aspect and steric hindrance (Table 4.9).
For certain compounds (Table 4.10). a special correction is necessary and the Slructure cor-
rection terms are done away with. We then have:
m:O,34I90+S+0.18473SI+~JI (4.92)
,
S",:£N/.lj (4.93)
j_ I

The translalion term c: varies with temperature aa:ording to the law:


({T)" ((T~)[I + a(1 - Y) + .8(1- Y)l] (4.94)
with:
Y '" exp (I - TI T~). a" 1.8746 lO-9T,; - 0,2464, .8" 2.2079 10-3 Th - 1.2179 (4.95)
where c(Tb) is the lranslation at boiling temperature at atmospheric pressure. It can be
estimated either from the density data. or the equation:
c(Tb ) '" -Q.236 1 Tb + 59.6102/11 1 + 5 (4.96)

where 5 is calculated by group contribution:


, ,
s" 2 N,C/ + 2 'tbCt (4.97)
io1 t_1
the groups and the structures are the same as those applied to the estimation of covolume.
The nllmerical \'alues for the increments are shown ;n Table 4.8. In the special case of
4. Cqwlions 01 Sme 133

cyelopentane and cyclohexane, it is necessary to OOlTcct the c(Tb) expraiSion by adding a


oolTeclive term Ac equal to -2,498 and -3.9711. respectively.
The equation of stale defined in Ihis manner has been applied to the calculation of
vapor pressure. liquid phase density. heat of vaporization. and specific heat at conSlant
pressure in the liquid phase. Special atlention;s paid 10 the range of low reduced tempera·
tures. and to high molecular weighl oompounds. The results are or a precision comparable
10 experimental precision,

Tab,," 4.9
Groop contributions an<! slrucTural incremc:nls for tile estimaTion
of tile fonn paramc:ter III (Eqs. 4.90 and 4.91)

.......
a,.
GTOUps M

0.04125
nil 0.04303
CH 0.02802
OuaTemaryC 0
Am.... lie r;rootJllI
CH 0.02618
Substitute<! C 0.03667
Condensc:d C ring
Struelures ...
0.00449

NO..-..u.- ll ' 0.04523


I,,, N,-IU for N," 7
Stlbstil.led .Iblta ml)) 0.00702
'I'" Nq .. N_ -6for N, .. 1t
'I_Z forN,>9
Riop
free Or OOfldensed (cu, or '''''rs,) C)"dopentyl
in tM naphlhentl -U.04O 19
free or eoodensc:d (c;" or "am-) eydohc"yl
in the naphlhenes ~.06837
Isopropyl Of t-Olllyl bound to an aromaTic
ring Of naplllhcnic 0.00746
Pol)....OIII.llo.s I'MO) 0.01812
'," I (or naphthalene and it< derivaTives
I, .. (~1)" 0.15 (N,:z .. 2 N,~) for the other
compounds (phenanthrenc, pyrene. ctc.)

(I) N, is the ll)lal numbor of carbon aloms.


(2) SUbstitutw alk~ withoul qUIIlernary carbons or contilt....... double substituTion.
(3) Nq ;,the nurn/)<"r of carbons from the principal cha'n. N_ the num~r of subs,i-
Tutions.
(4) ({ is the number of arolllllic nudei. N,:J. and N,~ are the number oIaromatic carborl
aTomS oomlllOfl to 2 Of 3 rings.
134

T~bko 4..10
Specific cvrr«t;w term wn for the calcuhuion
of the form parameter (Eq. 4.112)

Compound "m
Cyclopenl~"'" --().04322
Cydohc~al\(' -,(/.05143
ISQpropylc)'dohcnnc -{I.05022
fkn'.cne 0.02136
Toluene 0.00708

4.2.2.4 Eljuations of State for Rigid Spheres and Hard Chains


In a comparison of "rigid sphere'· molccules where the repulsion energy is either infinite.
wilen the particles are ill contact, or 7.<:ro. and deriving inspiration from st3tistic:althermo-
dynamics and molecular dynamics. Carnahan and Slarling [1969J propose an expression
ror the compressibility factor as follows:
J+/J+ljz_'lJ
Z", (I-II)} (4.98)

in which 11 is the reduced density:


(4.99)

and tI~is Ill" actual "olume of one mole or rigid spheres.


In uniting this expression ror the repulsion lCrm and the expressions proposed by van
der Waals or Redlich-Kwong for the attraction term ICarnahan and Starling. 1972]. we
obtain equations of state that may be compared to those having the van der Waals repul-
sion term. Such a comparison was made by Marchand 119841. who demonstrated that. pro.-
vided that the determination of the parameters for the tWO kinds of equations arc done in
the same way (without inclusion of the critical constraint. and by adjusting to the vapor
pressure and volume data). the n:sults were equivalent. Dohrn and Prausniu 11990] also
proposed a development for the Redlich-Kwong attraction term that is analogous to the
formula embraced by Bc!hart'/lII. [19851.
We may rightly conclude from this that it is nl:cessary to better take into acoount the
molecular form. and cxpand a less empirical attraction term. Many authors have done this,
and we ean cite the BACK equations [Chen and Kreglewski. 1977]. rHCf or "Perturbed
Hard Chain Theory" [Beret and Prausnit", 1975: Donohue and Prausnitz. 1978: Donohue
and Vilmachalld. 1988]. and COR or "Chain of Rotators" [Chien ('/ III.. 1983]. Without get-
ting into the delails of the expressions proposed by the authors of these equations, we point
out that the repulsion term. derived from the Carnahan Starling ICrm. has an additional
parameter. In general. il is adjustable and represents the length o( the molecular chain or
the degrees of freedom of the molecular structure. The attraction term was inspired by the
work of Alder tr al.119721. and we find a volume paramel<:r (already a part of the repulsion
term). and an energy parameter rcpresented by a "characteristic temperature". These three
parameters arc unique to each component and may be substituted. to a certain eXlent, for
the critical coordinates and the acentric factor. which we do not need to know.
135

These equations of stale hove recently OCto the subject of a comparative study
[Solimando. 1991]. We shall report (Table 4.11) the results that pertain to the calculations
of molar volume at saluration. vapor pressure. and the critical coordinates. These last val-
ues. as determined by Ihe equation of Siale. differ from the experimental values since the
critical constraints are not taken into account. For purposes of comparison.lhis table also
lisls the results obtained with Ihe "general cubic equalion~ ,expressed as PRe:
RT •
P= ,-,'-_-b-' - -,"'1-';'.'-c'~b"l (US)

in which the value for parameter ris the one corresponding to the Peng-Robinson equa-
tion. and the translation calculated such that the liquid phase molar volume al a reduced
temperature of 0.7 is restored exactly. For this last equation. the critical constraints hal'c
been taken into account.

T~bIe"'lI
Comparative =ulls of equal ions PRe. BACK. PHCf.and COil... Relative deviations (%1
of vapor pressure. molar volume in liquid phase at saluralion. density in the supererilical
regjon and absQ!ule devialion (K) fron, mlicaltcmperature lSolimando. 19911

-". ",
15v'_~
ST,
E'lUlltion
p' "/...
P., 0." 2A 3.'" -
BACK O.W 0.21 '.V W
PHCf 0.90 1.<» 5.53 17.00
CO. O.J() 0" ,.'" 5.03

We observe that the e'luations confer. in comparison with the PRe cubic equation. a cer-
tain improvement. particularly with regard to lhe calculatwn of molar volumes in the liq-
uid phase. This improvement is due in pan to Ihe abandonment of the critical constraint.
and the error on the critiC'll temperature is far from being negligible. In the case or the
PHO equation. it is unacceplable and leads to a degeneration of results within the critical
region. It is also appropriate to take into account Ihe erratic behavior of the BACK equa-
tion at low reduced temperature that impedes the calculation or vapor pressure.
In this comparative study. the COR equation stands out as superior. Its expression is
given below:
Z: I + (4tj_2tjl)/(I_ '1)3+0,5c'(a-I)[J'1+Ja'1-(a-I)'1zll(I-'1»)
,
+[1 + 0,5 r' (B o + B1PIT+ BlTIPI] L L
. IIlA_(T·'T)~(I,·III)" (4.100)
__ I "'.1

Wilh: (4.101)

BlI = 0:Z(X)95. B I '" 0.019. 6 1 : -0.0632, a = 1.078. and the universal coefficients A"", arc
provided in Table 4.12.
136

Tablr 4.12
A_ cocfrlcicnu 1m the COR equation IChicn ~I 0.1.. 19l13J

m ----.:... , 2 3 •
,, ~.04214 -1.12517 -0.809958 -o.6n378
-m,ll Wl.70!l -il3S.503 438.783
,
3 525,415
-859.803
-2566.20
4471.80
4398.77
-8598.81
-2482.01
S28':UIO
5 634.635 -3402.75 1 4(lI). 908 5 -5017.09
• -161.336 939.226 -2365.34 \784.58

To each componcnl correspond three characteristic parnmelcl"S, c', 'f'" and v·. for which
Table 4.13 provides the values for some hydrocarbons.

T.IM4.1J
Characteristic paramCICI1I for the COR equation ICh;e,n c' 0.1.. \9831

T-
Component (K) "
(an'·mol-1j "
Methane 151.19 20m 0
Elhan<: 226.48 JO-" '.899
Propane
,,·auI.ne
26353
293.52
41.37
52.11 •.'"
3,206

4.3 SPECIFIC EQUATIONS OF STATE FOR CERTAIN PURE SUBSTANCES

For a certain number of compounds thai are important in industry such as water, ammo-
nia. and the light hydrocarbons. numerous and varied e)(~rimenlal data are available
(-PYr' measurements. vapor pressure. heat capacities. speed of sound). Relying on these
data which have been SUbject to rigorous prior evaluation. one has pr~ equations of
state that are capable of reproducing them with exec:llenl precision. We may therefore
consider the results of the calculation to be "quasi-experimental" data.
The equations of slate are often spe:dfic if not 10 one component. at leasl to a small
group of compounds. They Icnd themselves poorly to the representation of mixlures. espe-
cially to lhe calculalion of vapor-liquid equilibria. Their form is relatively complex and
they conlain numerous paramelers. We shall provide some examples.
Younglove and Ely [19871 apply an equation 10 the light hydrocarbons thai is similar to
lhe Benedict. Webb. and Rubin equalion where p is molar density. expressed in moles per
liter. P is pressure. and Tis lhe lemperalUre. The equalion is wrinen as:

p=* A~P~+(* 8~pZ.'()eXP(_rpl) (4.102)


4. CqtJiHionsofSwe 137

The coefficient.s A~ and B~ are temperature dependent and the equation has a IOtal of
32 parameters. It may be applied to methane. ethane. propane. n-bulane. and isobutane.
The residual values relating to the thermodynamic properties (internal energy. enthalpy.
entropy. and heat capacities at constant volume and constant preS.'lure) as well as the speed
of sound ean thus be calculated.
By applying the Maxwell condition it ts also possible to calculate the vapor pressure.
However. the properties of the liquid and vapor phases at equilibrium (vapor pressure and
molar density) are provided by auxiliary (and explicit) correlations as a function of tem-
perature. and the result is practically identical.
llte range of application for this formula is large; up to 200 MPa and 600 K for melhane.
and 70 MPa and 600 K for ethane. for example. Precision is good: 0.2% for the calculation
of density, excepl in the immediale proximity of the critical point. The anal)'!iis of this pre-
cision as a function of the compound. the range. and the property is proposed by the
authors.
To bctler represent lhe critical region (natlening of the 1'(v) curve. and increase of heat
capacity al constant volume). Schmidt and Wagner [1985) apply an equation of state 10
oxygen lhat has two exponential lerms. In faet. il is a ~characteristic equatioll"lhat relatcs
residual Helmholt:r. energy;
A(T.p) -A'(T.p)
f'=- NRT (4.103)

to reduced mohlr density and the inverse of reduced temperature:


p T,
,. - and r=- T (4.104)
p,
It is wrillen as;
Il ~ ~

f' =- L n/o" r" ~ exp (_0 2 ) L Ir,o" r" + exp (-o~) ~ n,.o',f" (4.105)
1 I< ~

The equation has also been applied by Ely [1985J to carbon dioxide. by .klcobsen ef ul.
[19861 to nitrogen. and by Friend'::l al. fl989] to methane. It is derived from a more general
formula in which only the significanl terms have been retained.
The equation of state in the form 1'(T.p) is obtained through the derivative of
HelmhollZ energy as it relates to molar densily and. via the derivative relating 10 tempera-
ture. we obtain enlropy.enthalpy. and the heat capacities (sec Chapler I. Section 1.6.2). r-or
example:
(4.106)

A5 in the case of the Younglove and Ely fomlula.auJliliary correlations are proposed for
the calculalion of the saluraled phase propenies.
Haar and Gallagher 11978] applied a virial equation to ammonia lhat had 9 cocfficienlS
and a total number of parameters (taking into account the innuence of temperature) num-
bering 44. An analogous formula has been applied 10 water vapor [Haar ~ al.• 19l54: Kestin
~f aL. 1984: Dobbins cf al.. I988J.
138 I
It seems., however. thai flO analytic equation of Siale is applicable in a clearly satisfac-
tory way 10 the immediate surroundings of the critical point. II is therefore: n~ssary to
uS<: "scaling raclollo~. The IUPAC proposed formulas for carbon dioxide. for example,
IAligus el uf.• 19761 which combine an analytic equation and an equation specific 10 the
critical region. Nevertheless. lhey have one disadvantage: in the region where the lion-ana·
lytic ternl cannot be overlooked. the integrations necessary for the calculation of residual
values m\l5! be accomplished numerically.
[\ must be pointed oul that because of their precision. these formulas may allow for an
improvement of the Lee and Kesler method. If. for example. we are interested in light
hydrocarbon mixtures.. we may choose methane and /I·butane as the reference compounds
and calculate their properties using the Younglove and Ely formula. In this instance. preci-
sion will be higher th:m that obtained with Equation 3.25. finally. like Lee and Kesler. we
will interpolate as a function of the acentric factor.

4.4 THE TAIT EQUATION

The Tait equation [Dymond and Malhotre. 19881 is not strictly speaking an equation of
Stale. It is rather II spttific expression of the compressibility of liquids whose application is
limited 10 temperatures that are clearly lower than the critical temperature. It is ""rillen as:

II(P,T) '" v(O. T) { J - CIn [I + B;T) J} (4.107)

where II (0. T) represents the molar "olume at :tero pressure (practically the same as the
molar volume at atmospheric pressure). Parameter C is virlUally independcnt from the
nature or the component under examination:
C = 0.0894 (4.108)
Parameter B varies with lemperalUre. and the expression:
B=Bocxp(-BIT) (4.109)
is oflen used. Finally. the value of II (0.7) may be expressed as a function of the heat cxp:m-
sion coefficient a:
v(O.T) = I>oexp (aT) (4.110)
Values Bo. 8 1. t·o ' and a are specific to the substance being studied.
The Tait equation may be applied 10 mil(lUres as long as it is understood that its param-
eters are then composition dependent.

p'
4. fqu.JtionsolSl.lte 139

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HarmeR. A. KlIapp H (1900) Thr~""p"ramcl"r cubic equation of Slale for normal SUbslsl1CC5. Itld.
£"g. Ch"",., F""'/fJI11 .• 19. 291·29-1.
lleyclI G {1900) A cubic l"qu8lion of Slale "'11h extended range of application. I..: Cherniwl
£ngin~ring ThrrmlHlynamia. Newman SA (Ed.). P 17S.Ann Arbor Scicnoe.

.bcobscn RT. Stewart RB (1\186) lkrTTJQdynamic properties of nitrogen from lhe freezing line 10
2000 K 81 p~res up to [!XI) MPa. J. Phys. Chc",. R,f. /)Qla, IS. 735-909.
JacKhke M. Audiben S. van Canenghem P. llumphre)'5 AE. Jansen van Rosmalen R. Pellel O.
Schouten JA. Micheh; JPJ (19918) SimplirK:d GERG virilll expansian rOt field U$e. $PE
Production £"slnuring. August. Jso.-35S.
.hIcschke M. Audiben S. van Vanenghern P. Humphreys AE. Jansen ''3n Rosmaltn R. Pelltl Q.
Schouten JA. Michels JPJ (199lb) Aa:urate prediction of CQmp~ibility facton by the GERO
virial expansion. SP£ Produc/U)n £ntrinN'ring.August. 343-349,
Jullian S. Barreau A. Behar E. Vidal J (1989) Application of tlte SBR equBlion of state to high mol"",·
ular weighl hydrocarbon... Chnt!. Eng. Sci.. 44. 1001.1004.
KCSlin JV. Sengers JV. Kamgar-Parsi Rl..cvclt Stngers JMH (198<1) lhcrmophysical properties of
nuid HJOJ. Phy" Chem. Ref DDlu. 13 (1).175.
Marchand R (198'I) t.1",1" co",/X',h. JIJrlS 1/1 "giQn ."iliqur, drs rq"lJ/ions d 'bill fo"drn .." 10 Ihb>tk
dn .ph~tn ,I"m "'. &,,,
Ie I"mre d" "p"l.ion dt '''''' ,ItT Woo'" Bdilion~ Tedmip. Pari$.
Marlin JJ (1m) Cubic equ~tions of state· Which? Ind. F:ng. Chtm. FrmMm .. 18. 81·91.
Malhias PM. Copeman ThW (1983) EXlcnsion of ll1e Peng-Rubinson equalion of Slate to complex
mixlure", ev.luation o( t.... various fonns of the lucal romposiliorJ eonCC!p1. fluid Phoue Eq"WbriD.
13.91·1011.
Palel NC. Teja A (1962) A new cubic equation of Slale for nuids and nuid mixturel. CI,e,,,, F:ngng.
Sd,.37.463473.
Pc:neloux A. Raul)' E. Frett R (l9ll.2) A consislent rorrection for Rcdlich-Kwong_Soave volume$.

_.
fluid Phust EquWb...... 8. 7·23.
Peng D- Y. Robinson DB (1916) A new '''''O<OnSlDnl equalion of Slale-I,,". eng. Chnt!. F"m"'m .. IS.

l"rouSI P. Vera JH (1989) PRSV: The Slr)'jock.Vera modift<,;ation o( lhe Peng.Robinson equalion of
stale. "arameters (or otller pure compounds of induslrial interesL C..n.l. Ch"m. Eng.. 67. 170-173.
Rauzy E (1982) Les m<!tllodes simpld de: ealeol des ~quilibreli liquide:-vapcur OOIlS preliSion. Thesis.
Uni,,,,rsM d'Aix·Marseilie II.
Redlich O. Kwong JNS (1949) On the thermodynamics of solutions. V. An equation of Slale.
FUg3Cilie~ of galiCOlls solutions. Chem. Rev.. 44. 23l-244.

Reid RC (19il3) Retrosp"etive rommcnls on physical propen«:s correlations. fluid ('hAS<' IOqui/ib'....
13.1-14.
Rogalski M. Carrier B.Solimando R. PenelOUJlA (1990) Correlalion and prediction of physical prop-
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lS03-IS12.
Schm;dt R. Wagner W (1985) A ""w
form of the equation of stale for pure substances and ilS appli.
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141

Simnkk JJ. Un 11M. Chao KC (1979)Th( BACK equation of Slate and phase equilibria in pure- fluids
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t:ngn,. Sci., 27, 1197·1203.
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Un;vcrsil<! d'Ai,,·Mar$l:ille.
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I
5 Characterization of Mixtures

In the majority of cases. thermodynamics is applied to processes involving mixtures. It is


lhcrdore appropriate to examine the extem [0 which the methods applied 10 pure sub-
stances lend themselves 10 sr.;tems lhal are characleri7.ed by conditions of temperature.
pressure (or volume). and composition. In particular. we hope Ihal properties of mixtures
may be inferred from the properties of their components with the aid of simple and pre-
dictive rules.
The first step in Ihis endeavor consists of defining a convention thai allows for strict char-
acteriVltion of the various auribules that must be known. More precisely. we need to know
the contribution of each component 10 a particular property (volume,enthalpy,ctc.). and the
"potential" thai dClcnnincs exchanges of mailer. Using a defined sel of definitions and
mathematical equations, this characterization will provide a core structure into which we
may introduce the various thermodynamic models to be presented in the foHowingchaptcl1i.
So as not to lose sight of the physical reality of this structure. we will do our best to
eKplain it in terms of molt'C'lllar interaction concepts. As a matter of fact. lhe mixing
process is accompanied by a "redistribution" of attraction and repulsion forces that arc
exerted bet ween en lities of different chemical nalures.
This observation alone tells us that the simple and predklive compositionallaws thai
we desire are. in general. only an initial approximation.
We shall therefore point out thc deviations to lhese elementary laws or excess \·alucs.
The application of equalions of state to mixtures will be discussed later on (Chapler 8),

Compmition Ranges and Molar Values


Lei us assume Ihal all the componenlll of a mixture are known. The problems encounlered
wilh "complex" or "multicomponent" mixtures sueh as natural gases. crude oils.. and poly-
mers will be addressed in subsequent chapters (sec Chapters II and 12).
A mixture is now defined by the nature of its componenl$ and the quantity (number of
moles N,) of each one of Ihem, From them we derive the total number of moles N" and its
composition expressed as mole fractions. This composition is generally known as ,ti , If in
addition we wish to determine the physical state of a homogeneous phase, \\"e reserve the
notation XI for lhe liquid phase, and use y, for Ihe vapor phase.

(5.1 )
144

x = Ni (S.2)
, N,

Any extensive property (volume V, ellthalpy H, elc.) of a homogeneous phase may be


divided by the number of moles "'1lllin that phase. thus defining the corresponding molar
value (v./r. etc.).Throughol,lllhis chapler we shall oflcn use volume in uurcxamples as it is
the most concrete properly. but established equations may be easily generali7.ed 10 the
olher extensive properties.

5.1 PARTIAL MOLAR VALUES IN THE HOMOGENEOUS PHASE

5.1.1 Definitions. Main Equations

If the miXILlrt: in qucstion is divided inlo several phases, liquid and vapor. for CJlamplc. cal-
culation of its extensive propenies is tile Tcslll\ of the sum:
V'" VV + VI.
Therefore we shall examine the properties of a homogeneous phase. The question is tile
following: can we determine these properties from the properties of the mixture compo-
nents'!
Later in lhis chapter. we will state that the components of the mixture are iJllhe refe ....
enct'slate if they are pure. at 11K' IIlUIte tempel1lture. II tlte !lame pressure, llItd In lhe ume
ph)'sicaJ st.le as the mixlure. This definition hll5 the advantage of simplicity. but 115 ....e shall
sec. may presenl renain difficulties upon eakullition of the propcnies relative to this state.
It is. however. neccSS3l)' if ....e wish to allempt to answer the preceding question.
If we designate by the notation 1);.11;", etc. molar volume and molar enthalpy for each
component in this state. for ell.lImple. can we state?

(5.3)

We could assume that each component independently contributes to the propeny of the
whole. This is certainly false ~ause of the molecular interactions that occur between
compounds of a different nature. and due to the irreversibility of the mixing process that
does not take into consideration the rules of simple additivity for values such as entropy or
Gibm energy.
It is therefore necessary to more narrowly define these contributions: IlK'y are partUII
molar ..aIUft. Using volume as an example. we define the panial molar volume of compo-
nent ; in the mixture with the equation:

;; _('V )
j - aNI T,P.N/
(5.4)

This rorresponds to the variation of volume of the mixture produced by the addition of
component i. if all other conditions (temperature, pressure, amounts of other components)
are kepi constant.
145

We also note lhat any extensive value is a homogeneous function of the fir.;t degree as
related to tile number of moles,. If we multiply the quantity of each component by a
constant value. the extensive values are multiplied by this same factor. So:

We may therefore apply the Euler theorem 10 the cJl\ll:nsivc: values and write:

(5.5)

This e<juation, applicable to any extensive value. internal energy. enthalpy. enlropy.
Gibbs energy. etc.. rCij.Cmblcs the similar equation (Eq. 5.3) introduced preyiously as a
hypothesis (nOI Yerified) for Il1Qlar properties of pure oompooents in the reference stale.
Putial molar ...._ make up Ihe OJ"enllive component (.'()DtributiOfl for mldu"", prtJP"
erties. To do this, they .~nd fil"Sl and fOrf:mm;1 on 1M ...t"re of the romponent.
Jlo~ver. lhq represent .bo the k rnpoRse to lhe enril'onment" whaillUs component is
Mdecl, and are therefore re"leel to the uture or the other eom~b IIIId the oomposi-
tton or th., mh.ture. Of ooul"$t:.they are a rundion or lcompe...lute and ~re.
If the mixture is reduced to a pure substance. the partial molar value has as its limit the
molar property of the compound in the reference state:
(5,6)

If on the other hand, the mole fraction of the component approaches zero. the limil
value of the partial molar value is said to be at "infinite dilution~:

if;I/-+O (5,7)

We observe that it is generally under these conditions that the partial molar values dif~
fer the most from the properties of the component in the pure state, This fact is easily
explained by slating thaI in a diluled medium, the mole<:ular environment is completely
differenl from that of the pure substance.
Of course, the same equations that we derived from the thermodynamic properties also
exist for their partial molar values. For eXllmple:

(5.8)

(5.9)

5.1.2 Delerminalion of Partial Molar Values

If the property being investigated ~ known through a model such aI an equation of state.
for instance. the application of the definilion equation allows for the cakulation of partial
molar values relating to it. If this property is known from experimental dala. prior model-
ing is nef;:CSS3ry.
146 s. C""r~Cf<,..;r~tion of Mi.t"""

o EXAMPLE 5.1
MethalJe propane mixture: calculation of partial molar volumes

We shall illustrate this procedure by examining the panial molar propcrlies of


methane (l) propane (2) binary mixlllres. Table 5.1 shov.'S the yolumclric propcrlics
of this mixture at 344.15 K at a pressure of 1.377 MPa lIS a function of thc mole frac·
tion of methane. dcsignated Y/ since the mixlUre is gaseous.
T.bk5.1
Methane (I) propar>e (2) system.
Variation of molar .'olumc with composition
T_J4.l.t5 K. 1'", UnMPa

T, " ",~perimcntll.l " ealculaled


(cmJ·mol·tl (cmJ.mol- 1)
0
0.1 ''''
1791 ''''
"..
0.2
"" "'16
OJ
0"'
0.5
06
.
,"",
t 910

1967
.
"",
,'"
1969
0.7
0.8
1'}92
20t6 "..
2015
0.' 2035 2033
I
"'" ".7

In order to model the data. we will apply the Yirial equation of stale for pr~Ure.lrun·
cated after the seeond term. liS application to a mixture requires a second Yirial cod·
ficient expression as a function of composition. This expression is quadratic:
RT
II: Ii" + B(T.y) (5.10)

8 : L, LI Bl.jY1Yi (5.11 )

or for a binary mixture:


B : BI.ly 11 + 2 B1.2)'1)'2 + B1.1yf
It must be noted that in principle. the Yirial equation of state thus truncated may be
applied only al lower pressures. Here the choice was made to allow a less cumber-
some calculation, but the errol'S introduced into the results arc minor and do not
change Ihe significance of this example.
To determine parameters B I.I, B I,2' and 82,2 we apply this equation of state to the two
components. methane and propane. Their molar yolumt:5 correspond to compositions
YI : I and)'l : I respectiyely as w,,11 as to the equimolar mixture. We find:
81.1 : -31 cm J . mol- t HI.l ,,-93.5 cm J · mol-I H2J : -330 cm J · mol-I
Table 5.1 sho...·s that across the entire composition range. the experimental data are
well filted (it is understood thatlhe values thai sen'cd to determine parameters are
llot to be laken into account in this comparison).
'"' 1

I .. !!!

t, _. ·all 'DUIliI Der

l [
]
. If.,

.
J
d ri.

, .1 ~ B' 1 L
- ,B~

1 7 I,

'.'r::.ilLL.lfI f hr u II
148

Figure 5.1 illustrates the experimental data and the calculated values for the molar
volume of the mixture. as well as partial molar volumes of the f;:omponellts. The figure
invites commentary.
First of all. we note deviations compared to the behavior of the ideal gas as the value
of II' "" RTIP or 2078 em l . mol- l is represented on the figure. These deviations arc
larger for propane (where the reduced temperature is equalloG.9]) than for methane
(T, = 1.76). They depend. of course. on composilion.
The change of molar volu~ with composition is nOllincar."The mixture is accompanied
by II "dilalalion" and ilS calculalioo by linear combination of the molar volumes of the
twooomponents yields only a li~ approximation. On the OIhcrhand,lhc mixing law Ihal
we have applied to the scoond vinal coefficient 8 takes this phenomenOll into account.
Later on we shall see thai we arc dealing .....ith a ~nOfl·ideaIM mlxlllre ofMreal" gases.
On Figure 5.1. we have illustrated a graphical «lnstruclion melhod of partial molar
values for binary mixtures. Taking a mixture of composition Yl (Yl = 0.7 on the graph).
we draw the langenlto curve II(Y) down to the Yl abscissa point. h cuts across the axes
representing the components of the mixture (YI = I for melhane, and 11 =0 for
propane) on points where Ihe ordinale is equal 10 lhe parlial molar volumes and ill v,
respectively. This construction is valid for allY eXlensive property. Itlleed nol be oon·
sidered a means of achieving the most precise values for partial molar values of
COUT$e. but it visually represents their change and .....e will have occasion to relllm to it.

,-
~
._.- ._. -_._-- "
------
E'''''''
- ';

~
~
,
.,
,."

"0 02> OS 0.75 ,


y,

F''I''ft 5.1 Melhane (1) propane (2) s~tem. Varialion uI molar vt>Iume
and panial molar mllllllC$ willi oornpo6ilion. T. 344.15 K. P. I.3n MPa.
14.

It is therefore easy 10 stale the differences between the partial molar values of the two
components VI and vl and the molar volumes of the pure components "1° and v 1••
Between a partial molar value and the pure substance property there is only similar-
ity if the mi:lIlire reduces itself 10 a pure subslam:c. The other oomponents arc then
said to be "al infinite diIUlion'·. II is under these conditions that the differences
between partial molar values and the properties of pure substances will be generally
the greatest, as we have already slaled. This is also visible from Table S.2 and we note,
for example. Ihallhc partial molar volume of infinitely dilUlcd methane in propane is
greater than the molar volume of the ideal gas-In certain cases. (liquid phase mixllIres
of components wilh a very different molar volume. for example). it may happen that
one of the partial molar volumes has II negative value.
11lt' operatk>n thlot we hIove perfonned on Ihe .ulumetric at. may be apptied 10 lIny
exieMive .... ue. 11lt' mocklinj: sieps. the apptialtioft of lhe deftnition of p8rtiaJ nwblr
values. and theil' derh.. tiotl ~m8in ....lIyJ ....Id. We ~n'e that the _ or lefiiIi impor·
..... deviations I'rom the linear mixing bIws will be 1l1Ul8blted by dlll'en'ncu bet_
plU'Iild moIllr .1lItJel1l1ftd the properties <dlhe pure components in the merentt state.

In fact. if we hllve insisted on the definition and the calculation or the partial molar val-
ues. it is not beeause of the immediate pl1lctical importance for most or them. We are pri·
marily interCl>ted in the molar volume of the mixture and its enthalpy, and not in the par-
tial molar volumes of its components or the partial molar enthalpies. However, it is the
contribution of each component to the Gibbs energy or the mixture that we need to know
in order to determine the equilibria between phases or the chemical equilibria; thaI is to
say partial molar Gibbs energy. The relationship between this property and the other par-
tial molar values. however. warrants the importance placed on these values..

5,2 CHEMICAL POTENTIAL

5.2.1 Definition

Partial molar Gibbs energy is generally referred to liS -chemical potential- and symbolized
by Ill:
1l1"'(:~) (5.13)
I 1;"'' ',
The total differential of Gibbs energy is therefore expressed as:

dG",VdP-SdT+ L, IljdNI
or. by applying the Gibbs-Helmholtz equation:
G V H
dRT"'RTdP-RT2dT+~ (5.14)
150 5. CfwroKrerizdtion oi Mi./lJff:S

5.2.2 Equilibrium Condition Between Phases

The parlial molar Gibbs energy is lhe potential lhat regulates Ihe exchanges between
phases as well as chemical Iransformation!j" juSt as temperature and pressure 8TC the
potentials corresponding 10 thermal exchanges and volume variations.
For example. if we consider a mixture divided inlo two phases. liquid lind vapor. the
transfer of mailer between the [1000 phases satisfies the material balances relative to each
component:

and al the equilibrium condition:


(1.36)

Gibbs energy. an extensive variable. is expressed from Ihe contributions of each phase:

and therdore dGT./' '" dG1:r'" dG~p '" 0

The clcmcnuuy variations of the Gibbs energy of each phase 8Te related to the chemi-
cal potemials of each component in the liquid and vaJXlr phases:

and. taking into ottOunt the equation that expresses material balances:

dGr.r= L(JlF-Jlt)dN1L =-0


, ,
Since the transfers are independent (as opposed to what occurs during a chemical reac·
lion). we conclude from this that at equilibrium the dlemioll polen ti..l uf uch wmponenl
hilS the same "lIllle in ClIch ph.ase;
jjl.~"V
ri ~ rl (5.15)
I
This condition is of course generalized in the event that the system is divided into more
than two phases: liquid. liquid. vapor and solid. for example. Thus to the condition of mini·
mization (at constant temperature and pressure) of Gibbs energy. correspond the preced-
ing equalities. in a number equal to the number of components. There is. however. a Mloss
of information" because these equalities express an extremum condition. and not a mini-
mum condition such that "raIse equilibriuM may correspond to il. We will return to this
JXlint.
The previous equations impose constraints on the intensive properties of a system in
equilibrium (temperature. pressure. composition of each phase) on which the chemical
JXltentials are dependent. This may be seen in the rule of phases. If we say that" is the
l1umber of components in a system. and rpis the number of phases present. then the system
variance. or the number of intensi"e properties that may (and must) be givel1 to determine
the state is equal to:
(5.16)

p'
I
S. ChdrilClenZdrion 01 Mb,rUffS 151

5.2.3 Relationships between the Chemical Potential and


the Other Thermodynamic Properties

For the chcmical potential. it is appropriate lO present a number of relationships. FIrstly.


for a pure substance. it is the same as molar Gibbs energy. whK:h we will from now on note
lIS Pi"
Moreover. we shall apply 10 it Equation (5.5). established using volume and valid for
any extensive value:
(5.17)

5.2.3.1 The Gibbs-Duhem Equation


We rewrite the previous equation in the form:

£RT '" LN-.!!L


'RT
and consider the elementary variation of function GIRT:

G ,,", " ",


d-=,,--dNr+L..N;d-
RT I RT j RT

and. accounting for Equation 5.14. we obtain:


~ IlrV 11
LNrd-=-dP~ - dT (5.18)
I RT RT RT1

It is called the generalized Gibbs-Helmholt:l: equation and is most often applied at con-
stanltemperalure and pressure.Therefore for one mole of a mixture:

"
.L ...·d -
; I
",
RT
=0 al constant T and P (5.19)

The chemical potentials are not Independent. Their VllriIotioDli ....itll composition are
rdat«l by the: previoW/ ~ ...t1on. the: se--c:alled GIbb5-Dubc:m ~lUItkm. We shall mc:;t
often apply it to values derived from the chemical potentials to be discussed later on:
fugacity. activity. and activity coefficients. When these values are detennined experimen-
tally. the Gibbs-Duhem equation allows us to apply a test of coherence to them. In certain
cases, the equation also allows to complement incomplete data.

5.2.3.2 Dependence of Chemical Potential on Pressure and Temperature


The chemical potentials of the components of a mixture depend on pressure and tempera-
ture. We can easily fonnulate the following equations that correspond to those for a pure
substance (Eqs. 1.45 and 1.55):
(5.20)
152

(S.21)

(5.22)

If,as we emphasized earlier, values such as volume and enthalpy aTC rather used. in prac-
tice. for the overall properties of the mi;uure and not of the components. we see lhat in fact.
their partial molar values determine the variations of lhe chemical potentials with temper-
alure and pressure. and therefore have an important role in the evaluation of equilibria.

5.2.3.3 Relationships between the Chemical Potential


and the Other Thermodynamic functions
Chemical potential may be introduced from other tlicnnodynamic functions. It can be
shown thai:

Pi:O (:~I )r.P.N; ; (:~i )1~SNI '" (:~ tN,= (:~I tV.N1 (5.2])

Dt:monslration of these equations is simple. Forcx.ample. from cxprcssions5.14 and 133:


G",A+PV and thus dG=dA+PdV+VdP and
,
dG=VdP-SdT+LJ.l1dN;
we obtain:
dA=-PdV-SdT+ LP;dNi
, (524)

The chemical potential is defined as the partial molar Gibbs cncrgy. butthc cqualities of
5.23 do no identify it in any way with internal energy. enthalpy. or partial molar Helmholtz
energy beeau~ only the firsl derivation is done at oonstall1 temperature and pressure. the
definition conditions for panial molar values.
We are especially interested in the last of these:

.- ('A)
j -
-aNI T.v.....,
(5.25)

that will be applied when the mixlUre is represented by an equation of statl'" Ihal is explicit
in pressure.

5.3 FUGACITY

5.3.1 Definition

Like the Gibbs energy. the chemiCllI potential can be calculaled only from an arbitrary ori·
gin. Furthermore. it approaches -"" if the pressure or concentration approaches 7.cro.

p'
S. Chari>Clerizafion of Mj~fUre5 153

Finally. it is a relatively abslract value. It is customarily Subsliluted with fugacily. defined


for the comlXJnents of the mixture in the same way as for pure substances (Chapter 2.
Section 2.4.3. Equation 2.35). We shall first consider only the i$(llhermal variations of the
chemical potential:
at constant temperature: RT d In h = d/olj (5.26)
and $(I. between two states at the same temperature. the fugacity ratios will be subslituted
by the chemical potential differences:
(5.27)
If the properties are brought to standard state (pure substance. ideal gas slate. pressure
at 0.1 MPa). then:
(5.28)

where the value of rt


is equal 10 0.1 MPa.
If we wish to compare both the pure romponent and the component in lhe mixture. we
have: "
RTln /; =/01.. -/01; (5.29)

Finally. we note thai the equality of chemical potentials at equilibrium between phases
resul15 in that of fugacities:
(5.30)

5.3.2 Dependence of Fugacity on Temperature,


Pressure, and Composition

From the definiti<m of fugacity (Eq. 5.26) and the variation of chemical potcntial ....ith
pressure (Eq. 5.20). we immediately arrive at the expression:

Jln h ) Vi (5.31)
( ii"P T.1 = RT
In order to cxpress the dependence of fugacity on temperature. we will use expressions
5.22 and 5.28 and nole that the value of Ii is independent of temperature:
Jln li ) hj-h;
-
( aT /:; = - """'D"'r'f" (5.32)
RT
where hi is thc enthalpy of component i in the standard state.
Finally. we may apply the Gibbs·Duhem equation to fugacity:

L, x,(d In Ii),;,. = 0 (5.33)

However. al lhis point it must be pointed out that unlike what we had done for pure
substances. only Ihe variations of fugacity are defined. Indeed.....e have nol examined lhe
values laken by the fugacities of a mixture of ideal gases.
5.4 MIXING VALUES ACTIVITY

5.4.1 Definitions

It is appropriate to return to the comparison we made when introducing this chapter. We


compare the properties of the C()mponcnts of a mixture on the one hand when they are
pure. under the same C()nditions of temperature and pressure as the mixture and in the
same physical state. this state serving as our reference state. with, on the other hand, the
actual C()ntribution of each C()mponent to the properties of the mixture. For example. take
the difference between the value of the volume or enthalpy before mixing:
"L,N{v;. L,N{h;....
and its actual value. The difference is called the volume of mixing (therefore having to do
with contraction or dilatation). and mixing enthalpy (or heat of mixing):

(5.34)

Figure 5.2 represents the volume of mixing for the methane propane system calculated
from the data provided by Table 5.1:

;
~
! '"
:[ 20


j"
o +-___,----,-~--r-__,_-r---,--,______,-__1
o 0.' 0.' 0.' 0.' 0.' 0.' 0.'

.'1""" 5.2 Volume of mixing for methane (I) propane (2) .)'Stem.
T .. 344.15 K. p .. un MPa.

The mixing values are extensive properties. and their partial molar values can be
defined:
(5.35)
ISS

Of course. we similarly define the Gibbs energy of mix.ing. with the Gibbs energies in
the reference state denoted as I-l/:
(5.36)

and we use the expression 5.17 to write this equation in the form:

G,w '" LN/(Ill-p;) (5.37)

1'he difference between the chemical potentials in the mixture and In the reference
stale may bc expressed in terms of fugacity. We have:

coW '" RT~Nlln 7; (5.38)

The I'lllio of rugacil~ in the mlxlure lind in lhl' reference stile is called "Iletivity":

u/_,
t. (5.~)
f,
such thallhe Gibbs energy of mixing is also expressed by the equation:
(S.40)
and the partial molar Gibbs energies of mixing are expressed directly as a function or
activity:
",.")
( aN -
= g,!" = RT In u/ (5.41 )
f T.P.NI

5.4.2 Dependence of Activity on Temperature,


Pressure, and Composition

Activity is temperature. pressure. and composition dependent. It is easy to set up the fol-
lowing equations:
(5.42)

(5.43)

As for the variation of activity with composition. in general we must be content to apply
the Gibbs-Duhcm equation:

, . =0
LXi(d In Uih,. (5.44)

and remember that activity approaches I ir the mole rraction approaches I.


If "'e consider a mixture whose components are. if not indiscernible or without molecu·
lar interaction. but at least similar from the point or view of chemical structure and molec-
ular volume. such as mixtures or linear Cs·C; paraffins. or mixtures or benzene. toluene.
xylenes. we may.al least to a first approximation. predict that the mixing process involves
'5'

neither a large variation in volume nor appreciable heat. Since the inlcrmolcl;ular interac-
lion energks llrc similar for the pure components, their ~rediSlribulion" upon milling
causes no practical internal energy modification of this milClu!l:. Effectively, this is what is
observed experimentally.
Under these conditions.. and tllking into account the preceding equations thai describe
the variations of activity with pressure or lCmperatllre. we may also predict. at least ini·
tially,that this value is solely dependent upon composition. The ideal solution is thus intro-
duced. iF nOI defined.

5.5 THE IDEAL SOLUTION

Lewis 11923] defined the ideal solution using the condition of proporiionlliity between
rugacit)' in a milClurc and the mole fraction:
.
at given l'f- ",const.
T an d P . -
"
The fugacity of the mixltlre is reduccd to that of the pure subslance if the mole fraction
approoches unity. We therefore have:
(5.45)

It is of course the same 10 slate that in an ideal solution. activity is cqualto the mole
fraction:
(5.46)

Under these condilions.. as activity is independent of temperature and pressure. the vol-
ume of mixing and lhe enthalpy of mixing are zero:
vM,id '" 0 and "~,,.l '" 0 (5.41)
This is not true for entropy. Helmholtz energy. or Gibbs energy. Applying equa-
tions 5.40 and 5.46. for the Gibbs energy we have:
G"''w '" RTLNlln x/ (5.48)

II is possible 10 derive therefrom the Helmholtz energy or mixing:


AN,id '" GN,>J _ PVN,td '" G·~...J '" RT .... N·ln,l"-,
,,-, (5.49)
as well as the enlropy of mixing:

(5.50)

These terms convey the irreversibilily of the mIxing process that always involves an
increase in enlropy and a decrease in Gibbs energy.
There is of course a panicular case of a solution lhat is perfectly logical to view as ideal.
II is a miJtlure of ideal gases since the molecular inleractions arc 7.ero within such a mix-
ture. We arc therdore in a position to specify the value for fugacity in an (ideal) mixture of
157

ideal gases. The reference fugacity, of the pure substance that is. is therefore equal to the
pressure. Expressing the mole fraction as fl' we have:
f,' '" Py/ (5.51)
This equation allows us to final;:.!:c tile definition of fugacity.

5.6 CALCULATION OF FUGACITY

To dctermine fugacity for II mixture component. we use the expressions:


RTdln/;=dp; (5.26)

and: ('-orP;) T.N..N, -


-.-I
(5.20)

thaI both express the variations of Ihe chemical potential with pressure. In addition. oon5id·
ering Illat the ideal gas laws apply to a real fluid when density approa.::hes zero. we wrile:
lim (!;)p ..... o '" "Y, (5.52)
often wrilten as:
(5.53)

as it is understood that any fluid occupies an infinite volume as pressure approaches O.


The calculation of the fugacity of a mixture is therefore based. according to these equa·
tions.on Ihe knowledge of the partial molar volumes:

PYI
[, f'(-"i- -
RTin - '"
0
RT) dP
P
(5..54)

lbe ratio: /;
4'i '" PYj (5.55)

is the fugacity cocfficienl of the component of a mixture.


Application of Equation 5.54 presents a dilemma if the model that we are using dQC!;
not allow for specific calculation of partial molar volumes as a function of temperature.
pressure. and composition. Such is often the case when we use an equation of state that is
applicable to the liquid and vapor phllSCs, We shall address this problem in Chapter 8
(Section 8.3.2). which deals with equations of state applied to mixtures.

o EXAMPLE 5.2
Methane propane mixlure: calculation of fugacity in a mixture

To illustrate these definitions. we return to the methane-propane mixture that we


have already studied. We stated that the equation of state:

I II =
RT
p + B(T.y) (5.10)
i . -

,
i
p

.]

J
1. I

. t.
~.
. 1 '

0 o.
o. 7

au
159

5.7 EXCESS VALUES AND ACTIVITY COEFFICIENTS

5.7.1 Definitions

When studying pure substances. we empha5ized the fad that the ideal gas stale could
provide an acceptable approximation of the real fluid al low density. lind most of all. II
calculation intermediate. Similarly. with mixtures.. the concept of the ideal50Julion makes
up only one step in the calculation of the properties of II mixture. It would not be unrea-
sonable to confine oursclvCt; to Ihis onc step for II properly such as volume. II is an approx-
imation thai could be risk)' for cmhalpy. It is often unacceptable for the calculation of
phase equilibria, namely chemical potential or fugacity. The terms describing the diner-
ence between the properties of a real mixture and those of an ideal mixture IIrc called. if
we are talking about extensive properties. Mexccss values". As such. we have the defini-
tions for ell;cess volume. excess emhalpy. t:lI;CCSS entropy. and excess Gibbs energy. We
state that:

(5.51)
For these ell;tensive properties we have of course the same equations as for the thermo-
dynamic properties from which they are derived. for ell;ample:

(5.58)

(5.59)

""They have partial molar values. in parlieular. ell;ccss chemical potential:


, ('G')
11-/ =aN
/ 1;1:1',
"
=p/-p/ (5.60)

In the ease or volume. internal energy. and enthalpy. the exeC$S value and the mill;ing
value coincide. Indeed. the mixing value of the ideal solution is zero. We can indiscrimi-
nately state:
v = LN,v.~.;. V·... (5.61)

or: V=L,Ntv;.;.V£ (5.62)

The same is not true for entropy or Gibbs energy:

G .. L,N,p;.;. C·...

but: (5.63)

and similarly:
(5.64)

"d (5.65)
5.7.2 Dependence of Excess Values on Temperature,
Pressure, and Composition

The excess values are of cou~ dependent upon temperature. pressure. and composition.
For excess Gibbs energy. for example. we have:

(iJG')
-
iJT "'''';.N;
",-S'; (5.66)

(,~f)L,.:-~; (567)

(iJG')
iJp T.N'"
• ,. J '"
VI; (5.68)

Analogous equations may be: sctup for corresponding partial molar values. So:

('("!))",../11,. ,
aT ,
;-TI
hf
T
(5.69)

('"f)
iJp
r."N,.N/
_-, _ll j (5.70)

As for the innlJenee of comlXJSition. we may apply the Gibbs·Duhem equation:

"",r,dp,
, , ",0 at constant temperature and pressure (5.71)

5.7.3 Activity Coefficients

For the Gibbs energy of mixing. we have defined the activities (Eq. 539). We shall do the
same for excess Gibbs encrgy and introduce the activity coefficients:
/; Q j
1I"'""'<'ld '" - "" Yj (5.n)
f i :f j

or: (5.73)

These activity l"()CfficicnlS are rclalCd to the chemical polCntials and to the excess Gibbs
energy by the following equations:
p;",pj+RTln.rj+RTlnrl (5.74)

(5.75)
S. ChdrKrcriurion 01 M;>:I""'" 161

(5.76)

1lIererore.loI-"e lIIlIy expres.slhe ltdh'l1y roefficientll using 1111 eJ[1:ftII Gibtr.l eoe"l)' model
(Eq. !I.7!1) IIDd ronvetMly, the eX«M Gibtr.i energy rrom the IIctirity roeffidenu (Eq. .s. 76).

5.7.4 Dependence of Activity Coefficients on Temperature,


Pressure, and Composition

The activity coefficients are related to the excess chemical potentials (Eq. 5.73). We there·
fore afJPly Equations 5.69 through 5.71 to them and define the innuence of pressure and
temperature on this property:

Qln
( QT
x)
r.N•.N,
=-4kRT
(S.n)

and:
Qln X) _ ii," (5.78)
( fJP T:N"N, - RT

The Gibb$·Duhem equation is most commonly applied to the activity coefficients:

~.rid In y, = 0
, at constant temperature and pteliSure (5.79)

We must note here that. taking into account the low values of excess volumes. the devi-
ations from ideality in the liquid phase are generally minor and may most often be neg-
lected.

o EXAMPLE 5.3
Methane prop.me mixture: cafculalion of activity coefficients
By applying the definition equation. we can calculate the activity coefficients for
methane and propane in a mixture. as well as the excess Gibbs energy. The results of
these calculations are shown in Table 5.4.
The activities are to be compared to the mole fractions. and the deviations from the
ideal behavior are specified by the activity coefficient values and excess Gibbs
energy. Note that these deviations are small. which is normal. as the mixture is in the
gas state and has low density.
If we consider the nature of the ··model" selected to represent the variation or molar
volume or the mixture with the composition. it is nol surprising thal the deviations
from ideality are ~symm"tric··.
Yi(Yj)=y,(I-)'/). ;=1.2
1

"I

] ]

'7
"I

au
16]

Relationships between the Fugacity Coefficients

The fugacity coefficients provide a con,·cnienl indication of the difference thaI eltists
between the chemical potentials of a component and the result of tile cakulation per·
formed in the ideal gas Slate.
For a pure compound, we write:

RTlnl(J/= oJ'(oRT)
11/-.." dl'
0 (2.39)

....here 11;;5 the partial molar volume of the pure component.


For a mixture component. Ihe equation becomes:

RTln l
_ I '" j'~jj. _RT)
_ dP (5.54)
PYlo'l'
where ill is the partial molar volume of component i in lhe m;,Hure .
One might also define the fugacity coefficient of the mixture:

RTln41.. =RTln; = l j'( u- pRT) dP


0 (5.80)

with vas Ihe molar volume of the mixture. The fugacity cocfficienlS ddined illihis way are
of course different. but related by a number of equations. [n particular;

Y,-'" ~ (5.81 )

"
(5.82)

gF. '" RT (In /(I", - LX; In /(I,") (5.83)

5.8 COMPARISON OF TWO MfTHOOS FOR


CALCULATING FUGACITY

A cl~ e~amination of the pre~ding equations allows us to note that multiple approaches
exist for the same property. So in the case of chemical potential or fugacity. we may adopt
one or the other of the two methods that follow:
• Apply to the mi~ture an equation of stale thai lakes into account the influenCl.' of
composition using the "mixing laws This is the path chosen in the follo",jng calcula·
H

tions:
mixture volume Equations 5.10. 5.11 and Table 5.1
partial molar volumes Equation 5.12 and Table 5.2
fugacities in mi~ture Equation 5.56 and Table 53
activities Equation 5.39 and Table 5.4
164

- activity coefficients Equation s.n lind Table 5.4


- excess Gibbs energy Equation 5.76 and Table S.4
• Apply to the components of II mixture an equalion of stale without considering what
the i"nuenee of composition will be on the variables of this equation. The method is
complemented by the use of an excess Gibbs energy model. In order to ensure cohe-
rence with the first approach, the equation selected for the equation of stale will tJ.:,:
• RT
II j '" P + Bu{T) (4.19)

lind for excess Gibbs energy:


g£ '" (2 8 u - 81.1 - 8 u ) PXlXl (5.84)

By applying Equation 5.75. we would have derived the expressions for actiVity coeffi-
cients:

(2B U - B l.l-B U )P 1]
Yt=exp [ RT .f 2 • (5.8.5)

'l1lerefore the progression encompasses the following steps and equations:


- reference fugacities Equation 2.39
- excess Gibbs energy Equation 5.84 and Table SA
- activity coefficients Equation S.7S and Table S.4
- activities Equation s.n and Table SA
- mixlure fugacilies Equation S.39 and Table S.3
- panial molar volumes Equation S.31 and Table S.2
- voluml' of mi)tll.lre Equation S.S and Table S.1
or course, since the coherence between the two approaches is ensured by the choice of
thc excess Gibbs energy model. the results would have beell idelltical even though lhey
were obtaincd in a different ordcr.
When we look It liquid VIlpor equllibrla, \ltl!' \ltililuln I~ opportunity to apply tM two
appwadle! to Ihe calculation of fupcily. The riBt approadl ..ill esRnlially be ron~mecl
..ith equilibria at hil!:h pressure in systems havinl!: romponentJi ..ilh high VIlpor pltiSllre 01'
~upt'rcritiCilI components. The a«ond will be ~ al 50w pteSSlII'e 10 Qlculale tbe fupdly
of componenls of a Iiquid millture. Bringing Ihe two methods 10getber ..i11 finally allow for
expllJl:§wn of the nnge of application of equ.alion~ of Itale,
The following lable galhers the etpressions generally applied as a function of the phase
and the method applied.

T."s.s
E>:pl'C$5io<u for fugacity in miJuure~

Vapor I'llue liquid I'llaoc

First method Ir .. pYlflr If' .. pY,fI,'


Second method I"j " p·v
fI, YIYI" fl .. PflffiWtf
165

We nOle thai the 5eCOIId method is never applied 10 the vapor phase. The approaches
....ill therefore be characterized by the calculation method applied 10 the liquid phase. or
course, what we aTe Slating here for the calculation of fugacity is equally valid for the other
thermodynamic properties..

5.9 ASYMMETRIC CONVENTION: THE HENRY CONSTANT

Throughout the previous discussion. the mUlure properties were related to whal is
conventionally called -symmetric reference stales-. In IheK reference Slale$, wrincn as I:
for fugacity. for example. each component was pure. and under the same conditions of tern·
perature and pressure as the mixture. and in the gmt physicallllait.
It may happen that this Slate cannOl be 3uaincd. and therefore we cannot arrive at the
properties experimentally. Such is the case for electrolyte solutions. for which I'"e cannOi
conceive ions in the pure state. It is also the case for solutions containing ~pennanent
gases~ whose critical temperature is less than the temperature in question. A reference:
state in which these pennanent gases will be in the liquid state and pure. may. strictly
speaking_ be possible. but not attainable.
For such systems. it is easy to distinguish "solvents" rrom ~solutes"_ For the solvent or
solvents. we retain the reference state that we have adopted up to this point. and we have:

' t"
t ,=/)';x, (5.73)

For the solute or solutC$. we most often choose the infinitely diluted state. Under these
conditions. we define the "Henry wnstllnf' as the reference fugacity using the equation:

(5.86)

At a finite COflcentration we use:


(5.87)
r;
This equation defines as the activity coefficient for the asymmetric convention.
As opposed to the reference fugacity defined in symmetric convention. 1M Henry
romtaJIl depetMb DOl ollly Oil lbe lempenllure lind prasure, tNl abo oa the IUlure of lhe
IIOI~Dt or solftnls.

Bringing together Equations 5.73 and 5.87 allows us to relate the activity codficients
defined in symmetric and asymmetric convention:

t "
Y• -.. '
'-'i 'Ii (5.88)

and express the Henry constant as 1\ function or the reference fugacity and the activity
coefficient at infinite dilution in symmetric convention:
(5.89)
166 5. C"'lro>cr~";lilrionof Mixru~

Note that we apply this rormulation mainly for the solubility of gases in the liquid
phase.
We may also generalize Ihis as)'rnmclric convention in defining a reference state for the
solute. where it has a finite concentration. For example. we may usc molality (number of
moles per kilogram of solvent) equal to unity. We come across this convention in the study
of electrolytes.

REFERENCE

Lew .. ON. Randall M (1923) The,mod)"Ulm;a "nd /Ilr F,u £nugy of Clrtcmicol Sub.Ulmus.
McGraw·llill. New Yorl<.

p'
I
6 Mixtures: liquid-Vapor Equilibria

Having defined the principallhcrmodynamic properties at work in the characterization of


a mixture (partial molar quantities. aCllvity coefficients.. fugacity. etc.). it is reasonable to
first introduce lhe models lhal arc commonly adopted for Ihe prediction of these proper-
ties. These models are the models for excess Gibbs energy. and the mu:ing laws applied to
th" equlltions of state. Ho.....e\·cr.lh~ models have. most oflen. been developed to Tepre-
sem phase equilibria. It i~ therefore appropriate to first describe the two-phase behavior of
mixtures. Priority is given here to liquid-vapor equilibria with the understanding Ihal the
phenomena of liquid-liquid dcmixing. crystallization. and mulli-phasc equilibria will be
discu!;Sl:d further on.
Unlike pure substances.. according to conditions of temperature and pressure a mixture
may divide itsel( into several phases with different compositions. Liquid-vapor equilibria
occur upon exploitation of a gas or petroleum reservoir. They allow for the separation o(
mixture components via distiliation.The latenl heat accompanying the phase change is put
to good use during energy transfers. Familiarity with these equilibria is therefore a neces·
sary condition for the simulation and optimization of chemical engineering operal ions.
This k.nowledge is based aoo\'e all on uperimcntll dlllllt. Predictive methods exist. but
they arc supported by results of measurement for the determination of parameters that
are employed and govern their '·aljdity. We must emphasize this point. However. "'e will
nOI devclop the experimental techniques that must oflen be adapled to each case and take
into account the nature of tile mixture. and the ranges of pressure and temperature. For
furtller inrormalion. we may consult tile works of Abbou 11986]. Marsh [19S9]. Deiters
119861. and Holste [19861.
Similarl)·. the databllStS. bibliographic or numeric. that collect the results of these meas·
urements need to be known. The mOSl important was begun by the University of
Dortmund [Gmehling tf Ill.. 1978-1984J. but it is also worthwhile to cite that o( Kchiaian
[1973·1993]. which OO\'en; all the deviations from the ideal behavior. and provides data that
has been carerully monitored. Finally. the bibliographic database o(Wiehterle rf 01. [1973-
1985. 1993J is close to exhaustive.
We will describe the phenomena of vaporization (or condensation). discuss the general
principles for the calculation of liquid.vapor equilibria as well as the principal problems
that arise. and take a look at the various (onns that the equilibrium equation may assume
according to the nature or the mixture and lhe temperature and pressure condilions.

p'
168 ~. MixIure.;; liquid-V"IXIt" Eqviljbri~

6.1 DESCRIPTION OFTHEVAPORIZATION OR


CONDENSATION PHENOMENA

The description of a mixture requires knowledge of pressure. tempeTllture. and composi-


tion.ln order to graphically illustrate the phase changes. we shall first consider binary mix-
tures evolving at constant pressure, and then at constant temperature. Figures 6.1 and 6.3,
and Table 6.1 refer to the propane (I) II-pentane (2) mixture. Equilibria have been Cltlcu-
laled using the Soave-Redlich-Kwong method to be discussed in Chapler 8. Taking into
account the nature of the system, we can assume that the results of the calculation are very
close to reality,

Tab... 6.1
Liquid-vapor equilibrium of a propane (1) "·pentane (2) mixture:
al (p. 5 bar) isolMrs and (T. 300 K) isotherms

P .. 5bar T.300K
... (1 ) 'I...
COC) '-
(0C)
p-
(har)
p-
"",)
0."" 92.018 92.018 0.717 11717
0."'"
0.100
O.ISO
0.200
81.909
n.""
6002
56.849
" ...
89."'"
RU1J
83.456
1.125
1.537
,.""
2.375
0.152
O.19l
0."
0.'"
0.250 "'.223 81.106 2.801 0.9311
0.300 44.333 78.652 3.232 1.""
0.350 39.0116 76.081 3.668 1.071
0<00 73.376 4.109 1.152
0.450
0 .....
"""
30.174
26.363
70.518
67.482
4.556
'.00'>
12"
1.357
0.550 22.902 64.237 5.467 1.490
0.000 19.743 60.743 5.9JJ 1.651
0""
0.700
0.750
0."
16.1144
14.173
11.699
9.399
56.'"
52.no
48.110
42.80t
6.405
6.""
7.373
1.1l7O
....
"'''''..
2.898
0"",
0."'"
0.""
7.251
'.2.16
'.3J8
36.570
28.""
18.644
8.378
'.899
9.434
•.""
3.363

6.425
'''' 9"" 9.""
I.""
''''
6.1.1 Isobaric Liquid-Vapor Equilibrium Diagram

First. we shall cOIlsider the example of the propane (I) 'l'penLane (2) mixture at a pressure
of 5 bar.
Figure 6.1 indicates the compositions on the ab$cissa, namely the mole fradion of one
of the components with t l the entire mixture. Xl the liquid phase. and)'1 the vapor phase.
'69

""

,
,,
,,
'" ,
,,
--------
,,
,
~-----,--
,,
,• ,,
,,
o ,,
o 0.25 0.5 0.75 ,
Mole fraction ot propilflG

Fipn! 6.1 l!Obaric liquid-vapor equilibrium diagram (p. 5 bar) of


the propane (I) "-pentane (2) system.

Since the mixture is binary. the sum of the mole fractions ofbolh components must be one.
Hence. the mole fractions of the second component are readily derived from either ll'x 1,
or Yl' As a general rule. index I will be attributed \0 the most volptile component. with the
lowesl boiling point. or the highest vapor pressure.
On the ordinate. we have the temperature. Specifically on the abscissa axes 1 and O. we
have the boiling temperatures of the first and second component respectively. I.SoC for
propane and 92°C for n-penlane. at the pressure under consideration.
If we look al a mi:llIure with overall composition l, (ll .. 0.5 for eJIample), Ihis mixture
is a homogeneous liquid at low temperature.lf.at constant pressure, we provide heat to the
system. we first cause the tempera lUre of the liquid to rise. and reach the -bubble point" Tb
(at 26.4°C). where a fiM;t bubble of gas appcaB. At this point. the liquid phase evidently has
the same composition as the cnlirc mixture x1""bbl< = ~I' but the vapor phase appeaM; at a
different comJXlSition YI.IKobbt<. The vapor phase is generally richer in volatile component.
In this example'YI ",0.915. We say that the system is al ilS bubble point.
If we conlinue adding heat. we generally observe that temperature increases. and that
Ihe vapor phase simultaneously develops at the expense of the liquid phase. The syslem
splits itselfinto two phases whose compositions Xl and Yl differfrom that of the mixture as
a whole. These phases arc related by the equilibrium conditions of equality of chemical
potentials. prCMure. and temperature. In addition. the compositions of these phases. the
170

number of moles in the liquid phase Nt, in the vapor phase N V, and for each component in
the total system N I arc related by material balante$:
N1",NLx/+NvYi (6.1)

For example. a\ 4WC,x 1 '" O.34.y\ '" O.B3, and the vaporized fraction is equallo;

NV ZI-xi O.S -0.34


NL+N"
• • '" 0.33
YI-XI 0.83-0.34

In general. vaporization of 11 mixture progresses up to the ~dew point", The mixture still
verifies the liquid-vapor equilibrium conditions, but the liquid phase disappears. The coor·
dinates of this point are the dew temperature, the composition xi...... of the liquid phase.
and Y,,<l<.. " z; of the vapor phase. In the case of the equimolar mixture of propane. with
n-penlanc at a pressure of S bar. the dew lcmperalun: is 67.5"C and we have XI = 0.13.
If ""C continue to apply heal 10 the system. it b«omes homogeneous and we s.ay thai we
are dealing with a "superheated" vapor.
The description of the vaporization processes may be repeated for any composition of
this binary miKlure, The bubble points describe the "bubble curve" and lhe dew points the
"dew curve~. Tht.'SC two curves lhat dclimitthe two-phase range meet on lhe axes repre-
senting the pure substances as lhe bubble lind dew temperatures coincide (monovariant
system). Under lhe bubble curve is the range of the homogeneous liquid phase. lermed
"subeoolcd", and above the dew curve lhe zone of the "superheated" vapor phase. Inside
the lens.. the S)'$tem is in a partialvaporizalion stale. II is neither al its bubble point nor at
its dew point. and il is separated into twO phases: the liquid phase is at its bubblc point. and
the vapor phase at its dcw point.
Of course. lhe bubble and dew temperatures depend on lhe pressure. We shall ex.amine
this dependence using isothermal equilibrium diagrams.

Ternary Systems

It is possible to show the composition of a lernary syslem using a lriangular diagram. The
summits represent the components of the sySlcm. lhe three sides lhe binary systems
formed by 110.'0 of lhe lhree components. and lhe intcrior of the triangle the actuallemary
mixtures. In Figure 6.2. perpendicular to the plane of the lriangle.....e have the temperature
bordering a prism with the three lens shaped areas of binary equilibrium drawn over ils
surface at a given pressure. Inside lhe prism, we show lhe evolulion of bubble or dew lem-
peralures of lhe lemary mixlure. thus defining the corresponding surfaces..
The inlerseetion of the bubble and dew surfaces wilh an isotherm plane delel1Tlines two
curves along which lhe points represenling lhe mixlures at equilibrium correspond by
pairs.
A point situated between lhe two surfaces represenls a lwo-phase system while the
points representing the two phases in equilibrium are found on lhe bubble and dew sur-
faces.. and on tlte two curves corresponding to lhe lemperature invC1iligaled. They are
aligned wilh the poinlthal represents the entire mbllure duc to linear constrainlS imposed
by the malcrial balances.
6. Mi'lures: Liquid.vdp(X £quj/;bri~ 171

c
('~,:,:-:,:,~,:-, pa Po

, ,
,.,.,.
B
.. ~

,,
,,
,
,,
,,
,
, , ,: ,
-~--.-"--
, "


I'lJun' 6.2 l~ric liquid·VlIpor equilibrium diagram or a ternary mixture.

6.1.2 Isothermal liquid-Vapor Equilibrium Diagrams


Evolution with Temperature
Critical Point and Retrograde Condensation

The graph of the isothermal liquid-vapor equilibrium diagram for a binary mixture is sim-
ilar to the one that we just made for the isobar diagram.
FIgure 6.3 relates to the propane n-pentane mixture at 3CX) K. The pressures are drawn
on the ordinates and on the axes representing the pure substances: we have the vapor pres-
sures for the two components of the system. 10 bar for propane. and 0.7 bar for n-pentane.
At low density. the mixture is in the vapor Slate and pressure is low. A volume decre~ISC
causes subsequently a pressure increase. the appearance of a fil'!il drop of liquid at P = 1.36
bar (we are now at the dew pressure). then the partial condensation of the mixture that
will split into twO phases-liquid and vapor. finally the disappearance of the last bubble of
vapor at "= 5 bar (bubble pressure). and the compression of a homogeneOU$liquid phase.
172 6. Mixru.....: U"uid-II"1JOf fqui/jbri~

",--------------,

,
• -'-------
,,
, • ,
• ,,

, +--r--t-----,----1
, ,., 0.75
'"
t1prt 6.) lsollJ.crmalliquid·vapor equilibrium diagram (T .. 300 K) for
the propane (I) ,,·pentane (2) J)'$lcm.

On Ihe isothermal diagram. we find the equilibrium lens. but the positions of the liquid and
vapor areas and the bubble and dew curves arc inverted in comparison to those observed
on the isobaril: diagram.
II is interesting 10 examine the change of such a diagram with tempera lUre. and
Figures 6.4 and 6.5 allow us to do just that. They pertain to the ethane benzene system and
the equilibria were cakulalcd using the Soave-Redlich-Kwong method. as was done in the
previous example. For example, on this diagram we can follow the change of Siale of a mix-
ture with overall composition z\ = 0.7.
AI low lempcralu~. (10 and B~C. Fig. 6.4) the equilibrium lenses have the shape
describt:d previously. We note that the dew curve is for the most pari close to either the
P '" 0 or the YI = I axes. This shape is due to the large volatilily difference between the two
components. For the mix.ture investigated. the bubble (P = 23 and 31 bar respectively) and
dew pressures increase with temperature.
If the temperature is greater than the critical temperature of one of the components
(Fig 6.5). for eJl3mple 9tJGC. as the critical temperature of ethane is 305 K, the lens extends
only over a portion of the full composition range. Mixture II = 0.1 still has a dew point at
this temperature (4.1 bar) as well as a bubble point (P '" 16.9 bar). The bubble and de....
curves no longer meet at the l, = J axis.. but at a point corresponding to the maximum of
173

"'-,-------------,

,
,•
,,•
••
••
,•
o ------------_.!"""

r'l""" 6.4 botllermalliquid-vapor ~uilibrium diatp"llm (8_ 10 and


2S 0 C) for tile ethane (I) benzene (2) system.

pressure. AI this point. the liquid and vapor phases at equilibrium are identical in C(lmpo-
silion and in their propenies (density. enthalpy, entropy, etc.). 111&" ttK ullUI point of
1iolIa'd....,.,.. elpilllbi ..... lit lite pw,. lelllPf-,aID' e.
At 15Soc. the critical poim corresponds to the mixture II ,. 0.7. The physical change of
slale of this mixture as pressure increases will show subsequcnlly a homogeneous vapor
phase. a dew pc:lint (26.4 bar). and a two-phase mixture. Yel. we will n~ observe a bubble
point. and wilen the CTitical pressure (108 bar) i$ rca.:hed. the liquid-Yapor interface disap-
pears. and we observe the "critical opalescence~ phenomenon. At high pressures. the mix-
ture will once again be homogeneous.
At 175G C,the composition of the critical point of ethane is less than that of the mixlure
investigated. For Ihis mixture, the increase in pressure is slill evidenced by an inilial dew
point (P = 44.5 bar), by separation into lwo phases, but one observes that the liquid phase
proportion goes through a maximum and it is through a !iftOIId dew poctiIIt where. al high
pressure (P"" 106.7 bar), we leave the equilibrium lens to enter into lite homogeneous
:.eone. The mixture has no bubble point.
finally. at 210 and 23S°C. still for the II .. 0.7 mixture. there is no longer either a dew or
bubble point. and the mixture is homogeneous regardless of pressure.
,
174 6. Mi~rures: Uqui<J..VdpOI f""iljbri~

",---------------,

.. ''',,-"'"..,..'8.
"
155 "C

,, ,
,
,,
,,, , ,
, , 9.60,,¢
, , ,
,,
,
,, ''
,,
, , ,,
,

--- -- -- ,: i , ,

----- -- - -- ,
,
, ,,

o - -..-------~---- - p"
o 025 0.5 0,15
Mole IIllClion of e1tla1'lll

Apt 60S 15Olhcnnalliquid·~apor equilibrium diagram (8,. 60. 90,


155. 175. 210. aoo 235OC) for tile tthane (I) ben7.cnc (2) ~ystcm.

It is possible to depict Ihe change of lhe bubble and dew pressures as a function of tem-
perature for 8 mixture of fixed composition. This is what is done on Figure 6.6 fOf the
example discussed here. We nOllee the meeting orlhc bubble and dew curves allhe critical
point (the slope dP/dT for both curves is identical in this point),the existence of 8 temper-
1I1u~ extremum (crioondcntherm) and II p~ure nlremum (crioondcnbar. very close to
the critical poinl in the present example). Between the critical temperature and the erioon.
dcnlherm. for example at 448 K (175°C), the mixture being in\'estigaled has 1"'0 dew pres-
sures. and its evolution with decreasing pressures from the high pressure range where it is
homogeneous first shows a "high- dew point. then a liquid phase appears. a phenomenon
called relrogntdl' condl'llSIItion. then a ma;fimum deposit of liquid phase. and finally the
"Iow" dew point. Bubble and dew points delimit the two-phase region inside which this
mi;fture splits into two phases. lind outside which it is homogeneous.
In this same diagram, we have drawn the two-phase region of another mixture (~l :: 0.2)
for which the crioondenbar (T = 533.9 K and P = 68.2 bar) is clearly distinct from the criti-
cal point (T = 540.6 K and P = 67.8 bar). In the pressure interval defined in this way,atem·
perature variation foons two bubble points.
6. Mi~'ru~: Liquid. V"PO'" fqui/ibri.l 175

H'"

.... ..•...
...................... ~~ ..

"" "'" "'"


FiIUft 6.6 Ethane benzene.' !ystC'm: two-phase: e.'nvdopc: for two
dislind compos.ilions (solid lin",: Zj ,,0.7; dolted lioo: t I .. 0.2)
and l(l(:us of crilio:al points.

All of the.' critical points togcthe.'r determine the "mtK:al ,oinls locus". All the two·
phase envdopes fall within this line that extends rrom the critical point or the light com·
ponent to the critical point of the heavy component. Beyond the range ddined by the two
vapor pressure curves and the crilical point locus-the sYSlem is homogeneous regardless of
its composition.
Depending on the composition of the mixture, the cricondenbar may be found on the
bubble or dew eurve and we may observe two bubble or dew temperatures for pressures
between the critical pressure and the crioondenbar. In this last case. we are talking about
second type retrogrode condensation,
The qualitative description that we just gave relates to a binary mixture, For a ~multi·
component~ complex mixlure. the graph in the temperature pressure diagram remains va.lid
and we can draw the t"'O-phase envelope of a mblture of fixed composition. Retrograde
condensation phenomena may be obse.....ed, Such is panicularly the case for naturol gases
where the liquid deposit caused by a decrease in prC'ssure is observed during the course of
the exploitation of the reservoir (decrease in pressure due to the extraetiOfl of gas). in the
well (pressure drop during ascenl). and in the separation inslallatiOils at the well head.
It is imponant to note thaI the critical points locus may extend over a very large pres·
sure range, For example. this is the case if the mixture contains hydrocarbons of very dif·
ferent molc.:ular wdghts. So the critical pressure or the mixture that we were looking al
was 108 bar. and for the mixtures of methane with high molecular weight paraffins. such as
hc:xadecane ror example, the pressure reaches several hundreds of har. In particular, it is
clear that the critical coordinates of a mixture have nothing to do with its "pseudocntical"
coordinates. The first indicate a particular stale of the mixture. often experimenlally
176

observable. and the second arc merely paramctcT!i related to an extension of the corre-
sponding Slates principle. and without physical reality.
Finally.....e emphasiu thaI the graph we hove drawn corresponds 10 the simplest case.
According \0 the nature of the components and the appeal1lnce of liquid-liquid equilibria.
the two-phase envelope. lind the critical points locus may have morc complex forms. A
mixture may have no critical point. or may have several of them lsee Rowlinson and
Swinton. 1982. p. 191. and Kreglewslr.i. 1984. p. 1331.

6.1.3 Azeotropic Systems

Up 10 this point "'I: have considered it nomlalthat for a binary syslem the bubble and dew
lcmpt:ralures al 001151a,,1 pressure. or the bubble lind dew pressures al constant temper-
ature are monotone functions of the composition, This is in no way a steadfast rule.
Suppose we have two components having the same vapor pres:mre at a given temperature.
Either. for example. the bubble curve will present an extremum or it will be isobaric. In this
last case, the bubble pressure would be independent of compo!lition. and the system. at
least at this temperature. would behave like a pure substance from the point of view of
liquid-vapor equilibria. It is of course the first hypothesis that must be retained: the bub--
ble curve has an extremum. As for the hypothesis that twO components ha\'e the same
vapor pressure. it is in no way improbable. and examples of mixtures whose components
have close vapor pressures are plentiful. Such is the case for the cyclohcxane benzene
system that has a maximum pressure azeotrope. or even the hexafluorobo:nzene benzene
system with twO azeotropic compositions. one at maximum. and the other at minimum
pressure.
The appellr,iIlCC of 8R extremum of the bubble curve is not specific to such systems.
Deviations from ideality defined in the previous chapter mllY cause it as well. For example.
such is the case ror heptane dimethylfomHl.mide mixlUres rich in heptane. even though the
diUerence in boiling temperature is dose to 5O"C We can also cite the Cltrbon dioxide
ethane system. where the components have vapor pressures differing by 50% at IO"C.
In summary. this phenomenon may be caused by twO types of bchavion: neighboring
volatility of mixture components. andJor deviations from ideality.
We show thllt (Section 6.3.1) in this case. if the bubble curve has an extremum. so has
the dew curve, at the SlIme composition. At the extremum. bubble and dew pressures have
the same value. and liquid and vapor phases have the same composition. The liqlliod·"apoI"
equilibrium i5 therefore DOl seledil'e; we s.ly thllllhen' is lin "ueolrope". r"igure 6.7 i1Jus·
trates this phenomenon. We note that for the COmposilions in component J (the mOSI
volatile).lcss lhan the a7.eotropic composition. the vapor phase is richer in this component
than the liquid phllSC. in agreement with what was observed in the Mnonnal" case. On the
other hand. beyond the azeotropic composition. the opposite il; true and 5electivity is
reversed. Distillation of such a mixture that. in Ihis case. has a bubble and dew pressure
maximum. will yield the llZCOIropie mixture at the lop of the column, and not the most
volatile component. At lhe ~mom of the column. we have one or the other of Ihe two
components.. according to the composition of the original mixture. The llzcotropic phe-
nomenon lherefore constitutes a limit to the dislil1l1tion separation processes..
177

.., , - - - - - - - - - , ",---------,
• ,
,
• , , ,
,
,, , ,, " ,
,,
, ,, ,
,,
,,
,., ,,
,,
,.• ,,
,,
,., ,.,
+--,-,-,4
0,25 0.5 0.75 1.0 ,.,
.,+--r-~-__,---1
,., ,." ,.,
Mole fraction of herane

t1pft 6.7 Azcolropic liquid-vapor lXIuilibrium diagJllm of the benne (I)


acetone (2) system al SO"C (left A) or III atmospheric pre5$Uft (ri&"t. B).

A mixture having the a~eolrope composition therefore vapori7.es at a given tempera-


ture.like II pure substance. Pressure remains constant during vaporization. ~owevcr. if we
examine this same diagram 81 another u:mperalure. we will ob5e.....e that Ilhe azeoIropk
composition has changed. This change differentiates Ihe azeotropic mixture Ifrom the pure
substance. and allows us 10 cin:;umvcllI the previously discullsed sepllnllion limit. The two
oomponenls of II system having an azeotrope may be separated via two distillations work-
ing at different pressures. Figure 6.8 [Rawlinson and Swinton. 1982, page I08J oolJects the
data obtained by several authon. and shows Ihe change in waler COfTIJlO&ition of the
lIUQtrope as a function of temperature in the water ethanol ')'Stem. Table 6.2IOtsulti and
Williams. 1953] specifies these data for pressures higher than atmospheric pressure.

T.... ..,
Change in oompoo;ilion (mole fraction)
of the ethanol ....ler auoIfopl' with pt"C$Wfe

-~. Tempenllure ,
(MPa) (K, (ethar>Ol)
,.,.
""
...
0.'
00<' 385.75 '.ll82
,.'" "
437.35
0'"
00'"
>.. 455.75 '''''
,.."
"6

0.15
0
0


0.\0

i,
0.'"

'"
Temp«81ure (K) '"
.~6.X Change in the oomposilion otlho: water Clllar>ol azootrope: as a
funclioo of temperature [aa:oroin!\ to Ro..linson and S....intoo. 1'182. page l~l.

,
r.293.15K

, T.283.15K

••
~

i•
£
, r.26:).lSK

0.25 0.50 0.15


Mole fraction oIl11t1aoe

tltu,., 6.9 1...,lhermaJ liquid_vapor equilibrium diagrams for


the ethane (I) "",!'bon dioxide (2) system.
6. MixrlJie: UquitJ.-ViJ!lO' fquilibrid 179

It may occur that the a~eotrope exists only within a limited pressure range. In other
cases. the caroon dioxide ethanc mixture for example. it persists up to the critical lone.
Figure 6.9 sho,,",'S the isothermal diagram that fonns two separate lenses when the temper-
uture approaches the critical temperatures (both close to 3O"C) of the components.
Thc extremum of the bubble Ilnd dew points charaderi~ing an azeotrope is most often
a maximum. and corresponds to the "positive" deviations from ideality from the point of
view of the Gibbs energy (g£:» O. activity cudficients greater than unity). This is what is
observed for hydrocarbon mixtures. ur mixtures of hydrocarbons with polar sol\'ents. The
"negative'" deviatiuns from ideality can cause the uppearance of azeotropes with a pres-
sure minimum. which are often anributcd tu complexatioo phenomena (by hydrogen
bonding or hydration) in the liquid phase.
The rorrespondcnce between isuthennal and isobaric lI7,eotropic diagrams of a given
system is simple. For the azeotropic romposition.a maximum of pressure col'TCSponds to a
minimum of temperature. Figure 6.7 demonstrates this agreement. On the isothermal dia-
gram as well as on the iSQbarie diagram, the azeotrope is observed at 5O"C and lit atmos-
pheric pressure,

6.2 THE L1QUID·VAPOR EQUILIBRIUM CONDITION


THE EQUILIBRIUM COEFFICIENT

We have already shown that the equilibrium condition between two phases is expressed by
the equality of chemical potentials or fugacities. We have:
JJT=JJr or ft=f/".i=I,,, (6.2)
According to the nature of the mixture and the temperature and pressure ronditions.
this condition may assume various forms that result from the fugacity expressions and its
simplifications that we have already rome across.
If the temperature is less than the critical temperature of all the components. the vapor
pressure is defined for each one of them. Liquid phase fugacity may be calculated (sec
Chapter 2. Sections 2.4.3. and 2.4.4) by using:

with PIG representing vapor pressure, rpt the fugacity coefficient of the substance at satu·
ration, 'Ii the Poynting rorrection..l i the mole fraClion, and r/ the activity coefficient in the
liquid phase. For the vapor phase we have:

f i' -- p y,fl,
where Pis pressure'Yi the mole fraction. and ((IiI' thc fugaeit), coefficient in the vapor phase.
The equilibrium condition may be wrillen using the "cquilibrium coeff1C;enC'.thc ratio
of the mole fractions in the vapor and liquid phases:

K.• = !l
x (6.3)

180

Pf lilY'll
therefore: K· '" -
, P "r
- - T,L (6.4)

In this expression the first faclor is the Pt IPnlltio, the IIIO!iI i.porlalll put orille liqaicl
VlIIpor equilibrium aM'fnrir.l. We speciflClllly observe thai at first approximation this coef·
ficient varies wilh temperature like the vapor pressure. and is inversely proportional 10
pressure.
'The second pari contains the fugacity coefficient at saturation. f1J". the Puynling correc-
tion 'l'j. and the fugacity coefficient in the vapor mixture. Its importance depends on the
IcmperalUn: whieh governs vapor pressure and tlindon: the fugacity coeffICient at satu-
ration. The Poynting correction and the fugacity coeffICient of the vapor miJuuTC are tem-
perature and pressure dependent. Finally. we have the activity CQefflCicnl.
However......e nOlc that if all vapor pressures are low.so will be the IOlal pressure. Under
these conditions the equilibrium coefficient is expressed by the equation:

K," !l... .. ~pj rl' at low preMurc (6.5)


"
It is uodel'$tood that the -low preliSure~ restriction applies as much to tOial preliSure as to
the vapor preliSures. This CJ[pression could not be applied. for example. to the calculation of
the solubility of ethane in benune at atmospheric pressure. since the vapor pressure of
ethane has ~veral MPa.
Remaining within the framework of these last restrictive hypotheses. we s.ee that the
previous equation allows us to express the bublHe pressure as a function of the composi-
tion of the IKjuid phase:
(6.6)

So the shape of the bubble CUT\'e is directly related to deviations from ideality.
IllinaJly. we can negled these deviations (Til. .. I). we can state:
y- P'{
ideal solutions at low pressure: K_=_'._
P , x, (6.7)

p .. ~ P'{xj (6.8)
and:
,
This particular case relates to Raoulfs law. according to which "the partial pressure in
the vapor phase is proportional to the mole fraclion in the liquid phase~. We have seen
that the general Equation (6.4) splits the equilibrium coefficient into three {acton.. TIle
first is the P/,I P ratio., relating to ideal solutions at low pressure. the second. where we find
the fugacity coefficients and the f\>ynting conection. intervcnes if pressure reaches a few
atmospheres (according to the desired precision. etc.). and the third is tbe lIClivity coeffi-
cient in liquid phase. which may be very important (see Chapler 7).
We can also envision the case of ideal solutions under pressure. Thill hypothesis can be
valid as long as we do not approach the critical region. We nOie that the product that fig-
ures in the numerator of general Equation 6.4 is the fugacity of tbe pure substance in the
liquid phase:
"I. .... a
j _r{"j~

'
181

and the denominator is equal to the fugacity in the vapor phase. also for a pure substance:

t I" '"
p .,
!PI

So that for ideal solutions. the equilibrium coefficient becomes:

Itf. (6.9)
K,likal '" !;v

As we see. the hypothesis of ideal behavior results in the fact that Ihis coefficient is only
pressure and temperature dependent. It is independenl of composition. Note. however.
that as a general rule, one of the reference fugacilies that figure inl0 the above equation
relates to a hypothetical state: indeed. if. at pressure P and temperature T, a mixture is in
the liquid-vapor equilibrium state, ils ~lighl~ components arc vapor in the pure state. and
its Mheavy" components are I;quid~

o EXAMPLE 6.1
Calculation of the ideal solution equilibrium coefficient,
where the vapor phase is represented by the virial equation of
srare for pressure lruncated after the second term

If III is the second virial coefficient. 1)/ is the molar volume in the liquid phase. and P,~
is the vapor pressure. the fugacity in the vapor phase is.. using Equation (4.21). equal to:

fl'VZPllXP(~;)
Fugacity in the liquid phase is calculated by accounting for the Po}'llting correction:

!"L = Pf'
I i
exp (B,P")
RT
"p [V,L(P - Pf)]
RT

such thaI the equilibrium coefficient is expressed by the equation:

n,,,___
Pi' "p [(vt-Il;)(P-Pf)] (6.10)
P RT
Once again, we find as the main term thc ralio ofyapor pressure to tolal pressure. It is
oorreeted by a multiplier wllose effect is to bring tile equilibrium coefficients closer 10
unily. Indeed, since the second virial coefficient is negative (at least under tile rondi·
tions where this equation is applicable). we see that:

ifPf>P then I <Ki < Pf


P

and: ifr{'<p then Pf<K.<1


P ,
II
182

This resuh is casily understood if we consider thai the deviations from the Jaws of the
ideal gas. which are shown here by the viTial equation of stale. have a tendency to
approach the properties of the IWO phases. The selectivity of the liquid-vapor equilib.
rium. which is expressed by the ralio of the equilibrium coefl'icicnts of the substances
making up the mixture. is therefore diminished.
I
NOle Ihal the preceding equation allo...'S a vcry simple empirical representation of the
variation of Ihe equilibrium coefficients with pressure:

(6.11) I
Because of its simplicity. we will apply this method to the propane /I-pentane mixture
at 300 K studied in the beginning of this chapter (Table 6.1. fig. 6.3) even though the
vapor pressure of propane at this temperature (10 bar) makes the use of the vinal
equation of state truncated after the second term a bit excessive for evaluating fugac-
ity at saturation.
To calculate the vapor pressures. the scx:ond vidal coefficients, and the molar volumes
in liquid phase.....e shall apply the Lee and Kesler (Eq. 3.24) correlation. the
Tsonopoulos (Eqs. 3.18 to 3.20). and the Racketl method (Eq. 3.14).
At 300 K and a pressure of 3.232 bar. we obtain the results listed below (Thble 6.3):

T.bl~ 6J
Cak:ulation of Ihe ilkal equilibrium coefficients of propane
amJ ,,·pt:ntane at 300 K and 3.232 bar

Component
p'
(bar) (em J ·
H
mol-I)
.,
(C111 J '0101- 1) < ,
-,OJ
"""'~ '"0.725 OJ In
,,·Pentane -1203
"' 0.256

We can derivc the composilion of the phases at equilibrium by resolving:


'<I+Xl"']
Yl+)'2=1
)'1 = KIX I
Yl=K1:"~
The final resul1 is:

and therefore "'C ha\'c the following numerical values:


XI'" 0.302 and YI = 0.822
that we can compare to those provided by Table 6.1. XI = 0.3 IIJld YI = 0.83. for the
same conditions of pressure and temperature. As different calculation methods have
been applied. wc cstimatc that agrcement is excellent.

'to' pr' em
183

It is important to once again note that in this ideality hypolhesis..lhe equilibrium coef-
ficients depend solely on lhe nature of the component being examined. and the tem-
perature and pressure. The calculation of liquid-vapor equilibria is greatly facilitated.
We may allempl to apply the corresponding stalcs principle to these coerrK:ients.. as
did Hougen and Watson [1959. p. 941]. However. such correlations include the predic-
tion of lhe vapor pressures. a major factor of the equilibrium coefficient, that can most
often be obtained with beller precision by applying a vapor pressure equation that is
specific for the component in question.

In any event. Equation 6.4. which we consider general. is valid only as long as the vapor
pre5llure is defined. as .....e pointed out when the equation was introduced. In addition. if the
temperature is only slightly lower than the critical temperature of the ··light'· oomponents..
the calculation of their fugacity in the liquid phase utilizes a Puynting oorrection for a com·
pressible fluid. which is not negligible if pTe$Sllre is low. The re5lllt is only an approximation.
It is therefore preferable to evalllate the elements of the eqllilibrium condition by applying

K1 ""
.
one and the same model to the two phases.liqllid and vapor, namely an eqllation of state.

v ,'
0,
(6.12)

This expression is of course al$O valid in the specific cases that we have considered IIp to
this point.
In summary, we lui.... two p.IM for exprnsi0lthe liquid·... por eqllilibrium roemeient.
The first applies different models to the liquid and vapor phases. For the liquid phase. we
must calculate the vapor pressure of each component. the fugacity at saturation (using an
equation of stale in the vapor phase for pure components). the Poynting correction (llsing
density data in liquid phase or an equation of state for pure substances in liquid phase).
and finally. the activity coefflcicnts.. For the vapor phase. we must calculate the fugacity
coefficients of each component in the vapor mixture by applying an equation of statc to
this mixture. We call this path a "heterogeneous" method since. from the point of view of
its calculation. it mimics the heterogeneity of the mixture. This path has a number of
advantages.. It lends itself to the simplifications that we pointed out. its expression breaks
the equilibrium coefficient down into significant elements. and it may be adapted to the
case that is investigated. The main choice lies in the expression and the calculation of the
activity coefficients in the liquid phase. We shall see (Chapter 7) that the models proposed
to this effect Me numerous. and that some are predictive and take into account the molec·
ular structure of the $Olution. One of the main characteristics of this calculation method is
its flexibility. il is preferred for the calculation of liquid·vapor equilibria at low pressure.
However. the application of different models to the tWO phases in equilibrium docs not
allow for the representation of continuity of the physical states "'hen we appl"Q3eh the crit·
ical point. Then. heterogeneity becomes incoherence.
The second path. which applies the same model to the two phases present does not run
into this obstacle. Based on an equatioll of state. it leads not ollly to the liquid·vapor equi-
libria calculations. but also to the calculotion of other properties of the mixture: dellsity.
heat capacities. enthalpy. entropy. etc. at least as long as the equation of State is accurate for
all of these properties. It may appear to be more general since it may be applied as well to
,.4
tow as 10 high pressure. In fatl, it is less general because the CqU81ions of slate Ihal we use
(wilh the c~ceplion of the virial equation truncated afler the second term, which is only
valid 81 modernlc pressure and for lhe vapor phase) and the mixing rules that are associ-
ated with them (see Chapler 8) generally apply to apolar m;xlurcs only.

6.3 DEPENDENCE Of THE EQUILIBRIUM CONDITIONS


0N TEMPERATURE, PRESSURE, AND COMPOSITION

The change in the equilibrium C()Cflicicnt with conditions or temperature. pressure. and
composilion is. in general. complex and is investigated by applying tile equations Ihal we
have just cstablished lsce Rowlinson and Swinton. 1982. p. 1041. We shall examine two spe-
cHIC eases.

6.3.1 Dependence of Bubble Pressure on Composition

We wil1limit ourselves 10 II binary system. For a homogeneous phase, there are three inde-
pendent variables, temperature. pressure. and mole fmction of one of the components,
for e~ample in the liquid phase. or Yt in the vapor phase. At constant temperature. the vari·
x,
ation of the chemical potentials of the components is therefore wrillen as:

'.r)
(--
dYt
'y T.I' t
i", 1.2 in the vapor phase

and; ('.")
dX "t T.I' I
i = 1.2 in the liquid phase

However. at liquid-vapor equilibrium. the equilibrium conditions:

Jll'-Jlf" ",0 hl.2


allow for only OfIe independent variable. for example x"~ For any variation of x"~ since lhe
equilibrium condition is respected. we have:
d(/Jl' -/Jf"J = 0 ; = 1.2

or: "'_"l(aP.)
, dx
I
.('.r)
dY,
t
('Y')
dx T
_('.1") ".
r r.f' l aT I T.t'

The two preceding equations (i = I and i '" 2) are multiplied by Yi' and we take the sum:

IYt(ii't - ii n + Yz (iii' - iJ{H (',P,) r_T t

[( '.r)
• Y, - -
drt T.I'
.y, - - ('.:) ]('Y,)
dYt r.f'
--
dx T
('.1) l
"'Yl ~
art 1;P
('.1)
+Yl--
aT I T.I'
6. Mi~rurol: L;qukl-V.lpOf EquiUbri~ '.5
In this equation. we note that:

YI (a.r)
'l,,,
Un 1;1'
+Y2
(a.i)
~y
U I
-0
U'-

by applying the Gibbs Duhem equation. and that:


-v
Jivi +J,v 2 "'.,
-v V

We therefore obtain:

(6.13)

Furthennore. it is possible to express the first derivatives of the chemical potentials as a


function of the second derivative of the Gibbs energy. Indeed. we have:

g '" .r)j,ll + (1 - xl)~

and therefore, by taking into account the Gibbs Duhem equation:

(:) ",,-"
1 1;1'

These last two equations may Ix reliOlved in terms of j,lt and~:

j,l1=S+X,(:) ,,"
1 T.r

which when derived with respect to Xl yield:

aJ'> ) ( il', )
( -ax l T.P =-xl :i:1
ax l 1;1'
such that in the expression (6.13). the numerator is simplified:

Yl (,.1)
;:h l 1;1' +'2
(
to yield the equation:

op. (yl-.rtl(~!)r.,
t
(ar l =.," (Ylvr + "vI') (6.14)

This equation is applkable to any point on the bubble curve except the critical point. for
which the numerator and the denominator a~ simultaneously uro as the two phases in
equilibrium are identical.
spedrlC3[[Y. the equation allows us to lIlustrate the specirtcityofthe azeotrope that ....e have
already pointed OUt. koown as the Gibbs-Konovalow law. It states thaI any extremum of thi::
bubble curve causes idcntityof the compositions in the liquid and vaporphase.llnd vicc ver.;a.
6.3.2 Dependence of Bubble Pressure on Temperature
Clapeyron Equation Applied to a Mixture

Let us consider a mixture with /I componentS. of fixed composition. at its bubble point. As
previously, we observe tllat any simultaneous cllange of temperature preserving equilib-
rium is evidenced by the equations:

~r-Jll-"'O and d(~r-~h"'o


Multiplying each of these differential equations by y, and taking the sum, we obtain:
• •
L YldJJr", I_I
i_I
L YldPll
According to the generali7.ed Gibbs Duhem equation (Eq. 5.18). we can state:

• •
L -, L Yl -,
• p' ,. ,Yi II,
,. , h,
or:
,.L, y,d _ ' =
RT RT
dP-
RT2
dT

Moreover. the composition of the liquid phase remaining conSlant. we have:


L -L -I.
d PI =~dP- hi dT
RT RT RTl

and ultimately we Ilave the expression:


• •
(6.15)

It may be interpreted or established in the following manner: at liquid·vapor equilib-


rium. condensation of a mole of vapor of composition YI in a large quantity of liquid phase
with composition x, takes place at constanl composition of the liquid phase. This conden-
satioo is reversible and is accompanied by zero variation in Gibbs energy:
AGr.r = 0
This equation is preserved if the temperature varies. always remaining at the bubble
point:

therefore. we have:
AVdP-ASdT=O
187

Since Ihe Gibbs energy variation is ~.cro. we can replace entropy variation with the ratio
MlfT and obtain the e<juation:

(6.16)

which by its form is similar to the Clapeyron equation. However. here the 4 operator rep-
resents the difference between the properties of a mole of mixture with composition y/ in
tile vapor phase of the same composition on the one hand. and in a liquid phase with rom-
position Xi on the other hand. as specified in Equation 6.15.

6.3.3 Coherence Tests

The preceding general equations show Ihal Ihe liquid.vapor equilibrium data. tempera-
ture. pressure. and compositions of Ihe two phases. are not independent. They must also
satisfy the coherence testS that are the conscqucnteS of the Gibbs-Duhem equation.
Generally. these lestS may be applied only 10 binary systems and on the condition of using
a large number of isothermal measurements for which the precision has been estimated.
The oldest of these is based on the variation of the activity coefficients with composi-
tion. If we have:
g'
RT '" Q=x,ln r, +xlln l'i

we see that by taking into account the Gibbs-Duhem Equation (5.18) and the bond
between the mole fractions of a binary mixture:
x,+.r~=1

then:

This equation can be integrated bet....een the limits Xl =


the fact that Q(O) '" Q(l) .. O.....e see that:
° and x, = I. and accounting for
'f ,
."In-ldx,=O (6.17)

This condition may be verified graphically by lIsing the experimental vailies of the activ-
ity coefficients (the knowledge of which supposes a complete set of data: temperalurc.
pressure. and the compositions of the two phases). The area determined by the axis of the
compositions and the In rll'z curve mllst have an algebraic vallie or lera. This often used
criterion mllst be abandoned in favor of treating the data with a thermodynamic model
without bias. such as the Redlich-Kister equation (see Chapter 7. Section 72).
If the data are not isothermal. the generalized Oibbs-Duhem law mliSI be applied. nnd
the healS of mixing must be kno....n [sec Vidal. 1974. p. 4311.
It has also been proposed IBoissonas. 1939/thal. the Gibt>s-Duhem equation be
applied to the calculAtion of the bubble pressures by Slepwise gnphical integration. The
..8 1>. Mixw..,.: Llquid-V.opor fquilibtj~

resulls are oonlpllred 10 the experimental values. This method is applied with greal
diHicully and is hardly ever used.

6.3.4 Stability and Critical Poinl Conditions

The equilibrium oondition between phases. expressed by the identity of the chemical
potentials or fugacities. docs 1101 contain all the ~inrormalion"supplied by the second law
of thennodynami<'1 We used only the Gibbs energy extremum condition at oonslanllem-
perature aod pressure, llJld no[ the minimum condition. It is therdore possible 10 acquire
additional information conceming the stability of a state.
III order to be stable. the concavity of the surface representing the variation (isotherm
and isobar) of Gibbs energy with composition G(.f l • X2_ Xj. x•. etc.) must be oriented
toward the positive free enthalpics..
Let usconsider a supposedly homogeneOllss)"stem.charlK:terizcd by Ihe number or moles
of each componcnt NI.lInd GibbselH:rgy G.and break it down into two subsystems. The first
is made up of a small perturbation of Ihe initial system. and for each component conlains
NJ -i1Ni moles. lIS Gibbs energy will be calculated by a development of the second order:

i)G I "... (flc


C'=G-L "N i1N;+
<} J
2 L.L oN(JN i1N;i1Nj
i J

Similarly. for the subsyslem made up of i1N1 moles;

The glolml variation will thus be:

which must be positive whatever the i1N; variations. The quadrati<: formula whose vari-
ables are the second derivatives of the Gibbs energy with respect to Ihe number of moles
must therefore be positive definile.
For a binary s)'lltem. we shall derive Ihe simple equation relating to Ihe Gibbs energy of
mixing:
",M
.....,....-r- > 0
ox,
or
""
ax/ >0 (6.18)

Figure 6.10 illustrates this condition. It relates to the hexane (1) methanol (2) system at
298.15 K. and the cxcess Gibbs energy has been calculated using the NRTL model (see
Chapler 7) on the aSliumplion that the S)'lltem is homogeneous and liquid. To obtain Ihe
Gibbs energy or mixing. we applied equations:
/01 ~ •
G .. G-LN,~, (5.36)
189

0... , - - - - - - - - - ,

-<> ..

, -<>'"

'\;.
-<>'"
}. 8
, ,
-<>.'" , ,
, , M
~..AN
M',
-<>, p /
o"
-0.12
0

0.'

O. •
O.

0.' ,
UoIIl rraction at hexatWI

.lpno 6.10 Varialion or the Gibbol energy of mi~;ng of • n·lw:.u.ne


melhanolsystem in liquid phase as a function of the OOnlpollition.
(J. !Soc. Stability and liquid-liquid immoobilily.

(5.63)

or for one mole:

NOll' lhal the cun.'c for the Gibbs energy of mixing has IWO inflection poinu.. It:mlcd A
and 8 that correspond to the equation:
il'gM
=0
".
--2

Between these two inflection points.lhe concavity condition is violated. and a mixture
illu.mated by point M. for example. is unstable.
[f we studied the shape vf curve gN (x) wilh temperature. we could observe that at a
higher temperature the two inflection points approach each other and end up merging. We
are now al the critical point of the mixture that is characterized by the exprt'SSions;
iig'" i)-lgM
ax 2 ",0 and QX 1 ",0 31lhecrilkalpoinl (6.19)

In fact. the stability condition presented in thi~ way i~ necessary but insufficient.
Coll5ider line CD langcnlialto curve 8 101 (x) at two points. Its intcT1Cdions with a~es.1'l _ 0

p'
l' ..

~t:

b
t· '

(J f .. hr
191

the one we follow 10 establish lhe rule of phases from a balance of the intensive variables.
will be c~tendcd 10 the fllens!ve variables.
lei us take a mi"ture containing 11 oomponents. Since their quantity (number of moles
N;of each one of the components) is known. we can find the global composition z;.
In order to characterize the mixture and calculate its propenies. we must know Ihe pres-
sure. temperature, quantity of each of the phases prescnt (number of moles Nt. N V ). and
their compositions (xj.y/). in IOlal. 2N oj. 4 quantities. From these quantities. the models thai
we lITC using allow us to verify Ihal the equilibrium oonditiolls are respected (calculation of
chemical potentials or fugacities). 10 determine the volume. and all the Ihcnnod)'namic
properties (enthalpy. entropy. CIC.).
We use a material balance for each component (Eq, 6,\):

(6, I )

or n equations. The equilibrium conditions involve chemical potentials or fugacities:

I I, -I'
- i' ;= I." (6.2)

or equilibrium coefficients:
,
K; = ....!. (6.3)
';
or again II equations. Finally the equations for mole fractions:

for a total of2" + 2 equations.


In order for the problem to be solvable. we need two quantities 10 be determined. either
from those we ha"e listed, or from among the data that depend on them (total volume,
enthalpy, etc.).
So ,"'e an state Ihllt the lolal VIlriante (If Il 'lstem i~ ",qUill to Iwo, and this result CIln
~ expanded 10 • mulliphase equilibrium, There is no contradiction whatsoever with
the phase rule because (I) we have considered that the total quantity of each component
is known, and (2) by including the quantity of each phase from among the unknowns.
we have e~panded the variance to the e~tensive quantities, For example. we know
that for water al atmospheric pressure, the liquid·vapor equilibrium temperature is
fixed (intensive variance equal 10 onc). and equal to 10000C, but we cannot specify the
volume occupied. which. according to the extent of vaporization. may vary from 20 cm' to
30 liten.
Of course. in the choice of two data for the liquid·vapor equilibrium problem, intensive
variance must be respected. For a pure substance, from between these two data. only one
intensi\'c variable can be selected, and the same is true for a binary mixture at the three-
phase liquid-liquid.vapor equilibrium.
The fact that the total variance is reduced to two and is independent of the number of
components will allow us to briefly introduce the principal problems of liquid-vapor equi-
librium as a function of the nature of the available data.
6.4.1 At Given Temperature (or Pressure) and Vaporized Fraction

Since the tOlal number of moles is known. the quantities in each phase NI. and Nil are
derived direclly from the vaporized fraClion. The other unknovms are the pressure (or
temperature). and the composition of each of the phases.
l'wo importanl, specific cases mUM be mentioned. If the vapori1.cd fraction approaches
zero or 011I:. thell the composition of the disappearing phase approaches a defined limit
that can be determined using the equilibrium equations. while the composition of the
remaining phase becomes identical to that of the overall mixture. These limils Dre nOlhing
but the bubble and dew points of the mixture.
Finally. note that the problem can have no solution when the mixture contains one or more
supercritical oornponents.or have several solulions in the case ofrctrograde lXmdensation.

6.4.2 At Given Temperature and Pressure

The unknowns are the NI. and NI' quantities of each phase and their composilions. As
before. we rely on the material balances and the equilibrium equations 10 solve the prob-
lem. Of coun>e. we must nOle that the problem only has a "physical" solution if the data are
found within the inlerior of the two-phase envelope. We can say that a problem is indeter-
minate if the overall composition. temperature. and pressure of lhe mixture coincide
eX~lctly with the ueotropic coordinates.

6.4.3 Case Where One of the Data is a Thermodynamic Properly

Problems for which the data are the temperature or the pressure and. additionally. a prop-
erty of the system, may be perfectly conceivable in practice.
This case has been illustrated for the calculation of the pressure in a bottle of known
volume. containing a known quantity of liquefied gas of known composition, at a given
temperature.
Of COUI1it:. we musl also mention the case of expansion accompanying the partial lique·
faction of lhe mixture. Depending on the problem. this expansion will be considered iten-
thalpk or isentropic and the data for the problem are the final pressure and the value of
enthalpy or entropy,

6.5 CALCULATION ALGORITHMS

We will not go into a detailed description of the algorithms that have been proposed to
solve the liquid-vapor equilibrium problems. However. some examples will allow u.s to
spt-cify the principal dirfK1llties.
193

In general. the equilibrium ooefftcienls are a funttion of lempernlure. pressure, the


nature of all the components. and the compositions of the liquid and vapor phases. Several
of these variables are among the unknowns. such thaI the soilition to the problem is itern-
live.The discussion thal .....e provide below can undergo many modifications aimed at speed-
ing up the convergence of the resolution process. We can also mention some simplifications.
First, let us l(J(Jk at the case where these equilibrium l;Ql:ffic:ientll can be calculalt:d from
Equation 6.4:
K = rf I{Jf'1'j rl (6.4)
, p '/It

6.5.1 Calculation of the Bubble Point

The composition of the liquid pilose is identical to that of the mixlUre:

The equilibrium equations:


Y
Ki = -' (6.3)

and the condition:


"

are combined to give us Ille equation know" as the bubble point relationship:

L, K;.r;= I (6.20)

which must be validated.

6.5.1.1 Calculation of the Bubble Pressure


Since the temperature is known. we may {j priori calculate the vapor pressun..'S and the aetiv-
ity coefficients that figure into the expression for the equilibrium coefficient. The iterative
calculation will start by taking the vapor phase as an ideal gas miJllure (tl'Jv '" I) and forming
a preliminary hypothesis for prcs.~ure. P '" I bar for example. or applying Equation 6.6:

(6.6)

We therefore have all variables available to calculate the equilibrium coefficient. the
L
compositions of the vapor phase. and the sum KJxJ • This sum does not fulfill condition
6.20 such that these products. Kjxj • cannot be assimilated to the composition of the vapor
phase. They will. however. yield a preliminary evaluation arter normalization;
Kjx j
Y,' (6.21)
L KrJ
I
19'

The inilializmion accomplished. the iterative cycle will be continued by formulating a


new hypothesis for pressure based on the equation:

(6,22)

where: II is the currenl iteration.


By making usc of the: available data. the fugacity coefficients in the vapor phase may be
CIIkulalcd.
Each iterat;\'c step will in tum apply IIle preceding Equations 6.21 and 6.22 and lhe cal·
culation of the fugacity coefficients IfIt. until condition 6.20;s mel. Convergence is gener-
ally rapid.

6.5.1.2 Calculation of the Bubble Temperature


In this case. we do nol make use of the value of the lIctivity coefficients since they arc tern·
perature dependen!. We can make two temperature hypotheses corresponding respe.;:-
lively to the boiling temperatures of the mast volatile component. reduced by 20"C (in
anticipation of ,u:eotropc risk). aJld of the least volatile. iJlcreascd by WOe. For each
hypothesis. the sum r K,x/ will be calculated in an intermediate iterative cycle focused on
the compositions iJl the vapor phase. as the equilibrium coefficients are calculated from
Equation 6.4. This cycle will be initiated by taking the vapor phase as an ideal gas mi"ture
(lilt .. 1). followed by normalization of the K/x/ products. It quickly ends with the stahiliza-
L
tion of the sum K/A,. 'The values thus obtained for the two hypotheses of temperature
are usually that one is greater than I. and the other is less than I. and new hypotheses for
temperature are created by dichotomy. For each new hypothesis.. the intennediate iterative
cycle 1I1lowing the stabilization of the sum LK,x, will be repeated until condition 6.20 is
mel.

6.5.2 Calculation of the Dew Point

The composition of the vapor phase is identical to that of the mixture:


Y/'" X,
The equilibrium equations:
y,
K ,"-
x,
(6.3)

and the condition:

are combined to give us the equation known as the dew point relationship:

(6.23)
whieh must be validated.
195

6.5.2.1 Calculation of the Dew Pressure


We do nOI have the composition of the liquid phase and we therefore admillhal, to begin
the calculation. it is an ideal mixture, An initial pressure hypothesis alloWll for the calcula-
tion of the equilibrium coeflicients (Eq. 6.4). lind the y/K j ratios. These may not be
considered equal 10 the unknown oomposition in the liquid phase since the Equation 6.23
is not respected. and. even if il had been. they were calculated with the ideal mixture
hypothesis. Their nOrmali7.~llion:

'(i"'--
"
K,
(6.24)
~ Yj
I Ki
provides an evaluation oflhe liquid composition for the next iteration. pcrmilling the cal-
culation oflhe activily coefficients. A new pressure hypothesis is provided by the equation:

(6.25)

The Equations 6.24 and 6.25 as well as the calculation of the activit), coefficients ure
applied to each SUbsequent iteration. They nonnall)' converge rapidly.

6.5.2.2 Calculation of the Dew Temperature


This calculation will be pl:rfonned in a manner analogous to the calculation of bubble tem-
pl:rature. Initializalion ....ill invol\'e two levels of pressure. obtained from the vapor pres-
sures of the extreme components of the mixlure. For each pressure hypolhesis.an inlermc-
diate iterative cycle. i~lf inilialized by conceding the idealil)' of the liquid phase. will
allow the stabilizalion of the y/K; ralios and lhe calculalion of their sum. Through
dichotom)' we obtain the temperature at which condition 6.23 is validaled.

6.5.3 Partial Vaporization

As I'"e have seen. the lWO imposed data rna)' be the pressure and the temperature, the pres-
sure and the vaporized fractiOfl, or lhe temperature and the vaporized fraction, while the
unknowns lire, respective I)'. the vapori7.ed fraction. the temperalure or the pressure. as ....ell
as. of course. lhe composition of the phases in equilibrium.
The combinalion of material balances (Eq. 6,1) and the equilibrium conditions (Eq. 6.3)
allo"'s us 10 express the mole fractions as a function of these equilibrium coefficienls and
the numbers of moles in thc vapor and liquid phase:

,,' (6.26)
19&

To comply Wilh the oonstraint equlltions. combined in the form:

....e therefore write:

By dividing the numerator and the denominator of this equation by }:N1and using tile
vaporized fraction defined as:
N"
F"--NL+N
-;;". .,iI

we obtain the following equation thaI must be verified:

(6.27)

Proposed by Rachford lind Rice [1952J. this resolution method applies in principle.
whether lhe s)'litcm is ideal or not. If we need to account for all the clemenl50f Equation 6.4.
we may prllCl:cd by dichotomy around the unknown variable. the vaporized fraction. tem-
perature. or pressure. For each step of the iterative process. the equilibrium coefficients will
be evaluated by an intermediate cycle with the goal of stabilizing their Villue. and the sum:
L (Ki -1)zl
1+ (1(;- I) F V

will be calculated until condition 6.27 is validated.

6.5.4 Application to Ideal Solutions

In the case or ideal solutions.. the equilibrium codflcient or any componenl or the mixlure
is dependent only upon the nature or the component in question, the temperature, and the
pressure. II is independent or the nature or the olher components.and of the compositions
or tile two phases in equilibrium. It can be expressed as a function of the fugacilics in the
reference states (pure substance. same temperature and same pressure as the mixture, in
liquid and vapor states):
(6.9)

If. in addition. pressure is low, and ir the vapor pressures or all of the components are
low. we lhen write:
Kj=!J.... '" f1 (6.7)
" p
p; ~ f1x;
and:
, (6.8)
197

When the lempcralure appears among the data. the solution 10 lilt problem of bubble
or dew pressure is immediate. If nOI. iterations are performed 10 improve temperature
until Equation 6.8 i$ validated.
(n the ~e general case wllere. while retaining the ideality hypothesis. we mUSI lake
into account the deviations of the vapor phase from the ideal gas laWS, as well as the
Poynting correction. all the equilibrium problems will have an iterative !IOlulion. We shall
illustrate lhis point with an example.

o EXAMPlE 6.2
Calculation of bubble and dew pressures in an ideal mixture
Once again we mall consider Ihe case of Ihe propane "-pentane l)'lilem (Sedion 6.1.
Table 6.1. Fig. 6.1 and 6.3. Example 6.1). and for an equimolar mixture. we will calcu-
late the bubble and dew pres.sures at JOO K. The equilibrium coefflcientll will be cal-
culated by the method used previously (St:C1ion 6.2. Example 6.1).
TIle pressure (bubble or dew) will be initialized al I oor. and the iteraliol15 will be
condllCted by appli<:ation of Equations 6.22 or 6.25.

_...
Tables 6.4 and 6..5 below summarize the calculations.

Calculation of the bubble pressure of an equimolar propane II-pentane mixture at 300 K

P.lbar p .. 4.58 bar p. 4.97 bllr p .. 4.998 bar


Componenl

""","0"
..-Pentane
..,K

0.736
K .,
."
'-"II
,.on
K

0.1 'J.l
K .,
,.'"
,.em .,83
'.83<
K K·,
0.917
0.09\ S .",
K
1.82
K·,
0.9\
0.091
!Ki";r; 4.579 ,."" 1.0085 1.0009

T_ ...
c.lculation of the dew pn:saurt: of an e<;juimolar propane "·pentane milliurt: at 300 K

P .. lbar p .. 1.JS.4 bar p .. t378 btlr p. 138 bar


Component

"""'"~
..-Pentane
..,
K

0.736
,;K
0.0593
0.6793
K
.,OJ
O.SS4
,;K
0.0798
0.903
K
6.\56
,;K

,..., ""''' ,.....


0.9176
K
6.148
,;K
0.0613
0.9186
ll;lKi
."" 0.11824 0.9988 0.99992

These results are compared to Ihose shown earlier on (Table 6.1): P_= 5 bllr and
P_=I.36bar.
We can estimate Ihe agreement to be very .satisfactory even though the thermody-
namic models that were applied are different.
Of course. the calculation mode would have been identical (Of a mbtture containing
more than two componenl5.
198 lo. Mix'u",s: Uquid· v"P"'" fqui/ibri..

o EXAMPLE 6.3
Part;,,1 v.lporization .1t given temperatures and pressures
The unknowns are lhl." ~aporizcd fraction and the composition of phases in equilib-
rium. The equilibrium coefficients are kno"'n because of the ideality hypothesis. and
will remain in~arianlthroughoUlthe ilerations. such lhat in Equalion 6.7:

'" (K. -1)l'


£. ' '-0 (6.27)
1+(K j _l)F V -

only the \'aporized fraClion is unknown. This equation is reduced to the resolution of
an eltpression of degree /I - I for Fl" where II is lhe number of CQmponcnts. We will
determine its rOOI. which should be between 0 and I. If lhere is no rOOI lhat corre·
sponds 10 lhis partial ~aporizalion condition. it then follows that lhe mixture is in the
subcooled stale (F v < O).or is a superheated vapor (F V > 1). In the example below we
gi~e lhe calculalion inlcmlCdialcs for se~cral ~aporized fraction values.

We wish to fractionate a mi:l(\ure in one lheoretical stage such lhatlhe ~apor pressure
of the liquid phase obtained does nOI exceed 3.5 bar at 300 K. The composition of the
mixlure and lhe ideal equilibrium coefficienls (calculaled by applying Equation 6.10
according to the example used in Section 6.2. Example 6.1) are provided in Table 6.6.

T.ble 6.6
Comp05ition of a pn'.>f>"ne 1I.~nlane mixlun:
un<krgoinlt panial 'lIporiullion. and th<: equilibrium
coefftciems of the wmponcnts al 300 K and 3.5 bar

Component , K

Propane
/I·Buta""
bobutanc
0.2
03 ""
o.noll
0.' "lO6
/I.Pentane 005 0.2~1
lsopcntane 0.05 0.3140

Al the end of a partial vaporization where lhe lemperalure and pressure are 300 K
and 3.5 bar. we obtain a vapor phase lhat will be al ilS dew point and a liquid phase at
its bubble point. and whose ··vapor pressure" or bubble preSSUrl." wililhercfore be in
line with the imposed specification. Of course. Ihe mixlure ilSclf "'ill be neither at ilS
dew point nor ilS bubble point.
We shall apply Equations 6.26 and determine its ~alue as a function of the hypothesis
made for the vapori7.cd fraction:

Table 6.7 Ix'"low lists the results of thesc calculalions.

'to' pro em
II'

l..iO]mpi[)lII1'~en.t

t 1
200 lio. MixrlJn.'f: tiquid.VdpOt [quilib/id

If between the two data given for the calculation of the liquid·Yapor equilibrium there
is a quantity such as volume. entropy, oc enthalpy that does not figure into lhe equatioru
for mOlerial balance and equilibrium balance. the resolution proccSll may then require a
double itcr~lion, even in Ihe case of ideal mixtures. We shall illustrate this in the next
cnmple. It is similar to the example in Chapler 3 (fuample 3.2).

o EXAMPLE 6.4
Calculation of equilibrium a/ given temperature and volume
200 grams of a propane (10% molar). /I-butane (40% moIR.). isobulane (40% molar).
n-pcnllmc (5% molar). and isopenl3ne (5% molar) mixture lire contained within a
oollie having a volume equal 10 one litcr. We wish 10 know the pressure. the relative
amount, and tlie composition of each of the liquid and vapor phases al JOO K.
To solve the problem.....e need to have a(;Cess to a calculation method for equilibrium
coefficienls, and for volumes. II is not necessary Ihatlhese twO methods are absolutely
CQherenl. In this case. wilh lhe hypolhesis of ideal mixture. the equilibrium coeffi-
cicnls will be calculaled according 10 the method used in the preceding examples
(Example 6.1. Equalion 6.10). Proceeding in this fashion. we .....iIl delcrmine lhe sec-
ond virial coefficients B, for each CQmponenl. as .....ell as their molar volumes in thc
liquid phase "t. Using Ihe terms v':; and v:; for the molar volumes of the liquid and
vapor phases, .....e can write in aCCQrdance with the ideality hypothesis:

therefore:

We shall p.:rform the calculations for onc mole of mixture. The volume specifICation
is then: 1
J
I ) ' " 290.62 cm · mol-

A prior calculation allows us 10 kno..... the bubble and dew points of the mixture. and
Ihe CQrresponding molar volumes:
bubble point P., 3.56 bar "'" 103.9 em) . mol-]
dew point P '" 2.60 bar II .. 8892 cm J · mol- l

Since the volume imposed is between these t.....o limits. the mixture is in the two-phase
state. To specify this stale. we Shall proceed using su(;Cessive hypolheses for pressure.
For each hypothesis we will solve the problem of partial vaporizalion at the given
temperalure and pressure as in the prce:eding mathematical example. and for each of
lhese intermediate calculations, since we have the vaporized fraction. we will calcu-
late the molar volume of each phase. as well as thaI Qf the mixlure. The succes.sive
pressure hypotheses are performed by dicllQtomy.
p

.j7
~

i- ,
~,

i P

P'= p~ . '\V~I
-- J ,

-
,~

~
I'
I
"

It

h It
202 ~. M,·.twes.' Liq<JkI·V"fJO' Equilibria

o EXAMPLE 6.5
C.l/culation of the dew pressure in an acetone (y 1 = 0.5982)
wa/er(Yl = 0.4018) m;xtureat 323. /5 K

The unknowns are the composition of the liquid phase and the pressure. In Equa-
tion 6.4 the vapor pressure and the fugacity coefficient lit saturation are filled by the
data. They will be calculated by applieation of the Antoine Equation. and the virial
equation of state for pressure truncated after the second term. The second vinal coef·
flCient 8 will be calculated by the Tsonopoulos method (Chapter 3. Section 3.2.2.1).
The rcsulls (Table 6.9) arc as follows:

Table 6.,
Vapor pl'C'Mures and!le«>l1d viriat coefTlCientl
of acetone lind wat..r at 3D.IS K

Component P1 B,
"'1
(kPa) ("",Jlmok)
Acetone
Water
81.332
t2.326 -''''
~71B
O.9S9
0.""

An initial pressure hypothesis is made based on the ideality of the liquid phase and by
assuming that the vapor phase is an ideal gas:

~ oc; :;a.X/oc;;
We find p" 25.03 kPa.x I '" 0.1841..1'2" 0.8159.
Furthermore. we must calculate the Poynting correction and the activity coefficients
as a function of these values that change during the process of iteration.
The Poynting correction will be calculated using Equation 2.41. with the molar volume
in liquid phase being estimated by the Rackett method (Chapter 3. Section 3.2.1.2).
The activity coefficients will be obtained using the NRTL model (Chapter 7.
Section 7.6.2). and the values for the variables of this model will be taken from the
data bank established by Gmchling and Onken 11978]:
C ll :2716J . mol-I, C2t : 4359 J ·mol- t . (111"'0.4927
Table 6.10 below summarizes the calculations. As specified. for each pressure hypoth-
esis., the values for the compositions in the liquid phase are obtained by an intermedi-
ate iteration cycle that normalizes the ,/IKj rali06, withoul change in pressure. allow-
ing for stabili7.ation of the compositions. After stabilization. pressure is adjusted by
application of Equation 6.25:

(6.25)
~'i UI, ':U, I-

O£",fio,irT'£!j,d t

tn,li.
?I
K: --
~i
204

from its critical point (whose coordinates are generally unknown). Yet we have observed
and it can be demonstrated. lhal convergence. of this procedure in $Orne caseJi is very stow,
and Olher methods have been developed spedrlCally for the "homogeneous" models. A sim-
ilar equation of slate s.imuI18r>cously describes the liquid and vapor phases. However, it ill
also applicable if differclll models are anributed to the two phase5 in equilibrium.
The first of these simultaneously solves all of the equations imposed on the system. It
was proposed by Asselineau f'f ul. [1979] and Michelsen /1980].
We have seen that the equilibrium slate WlIS determined as 5OOf1 as Ihe values of IWO of
the variables (temperature. pressure. quantity of each of these phases) Of Ihennodynamic
properties (volume. enthalpy. elc.) were fixed. We shall denote these values r. r. V". and
11'. If n is the number of component$, we have alSol) seen lhat the material balances. the
equilibrium equation$, and the constraint equations yield 2n -+- 2 equations for the 2n -+- 4
variables. According to the type of problem. twO of the equatiom such as T - r "" o.
r- r "" O. NY _ NY. "" 0, v-v· .. 11. H _ H· = O. etc.. complete Ihe s~tem. This is not linear
as the products of the number of moles times the compositions ligure into the material bal-
ances. and as the e'luilibrium equations most often involve the mixture fugacity coeffi,
cients or the activity coefficients. and the expres.~ion for thcse quantities as a function of
temperature, pressure. and composition. mllY be complex. The same is true for the volume
or enthalpy expression. We Iherefore apply the NeWlon method for the resolution of this
2n -+- 4 s~tem. which requires prior determination of the expressions for the Jacobian vari,
abIes of this system. namely the derivatives of eaeh one of Ihe equations that we want 10
solve ,.ilh respect to thc variables (T. P, NY. NI., XI' YI)' expressions thaI are dependent on
the models applied to the mixture (aClivity coefrlcients. equations of state. etc.). We note,
however, that from one problem to the next. only the last two equations vary. Their nature
is related to the type of problem we want. such that the method has a degree of apprecia-
ble generality. It was introdl/oCed by Asselineau .,1 at. 119791. After resolving the problem. a
simple extension allows for the determination of the derivatives of the equilibrium condi-
tions relative to anyone of the variables. Of course. this kind of system may be simplified
in specific cases of bubble point. dew point. or partial vaporization at given temperature
and pressure.
A second set of methods is based on the minimization of the Gibb$ energy and prior
study of the stability of the s~tem using the method called "tangent plane".
Proposed by MiChelsen [1982a, 1982b, 19851. it was the subjeCl of many developments
INghiem, 1985. Agarwal rt IJ/., 1985]. and we shall introduce some of its principles with an
example for the Cllk:ulation of liquid· vapor equilibria using an equation of state (Oiapter R).

6.6 SOLUBILITY OF GASES IN LIQUIDS

To finish up. we consider the specific case of systems made up of"pennanent gases". com-
ponents whose critical temperature is below the range of temperature under examination.
and "solvents', components whose vapor pressure is low within this temperature range.
We wish to determine the solubility of the gases in the liquid phase as a function of tern·
perature and pressure.
205

Of OOUBC. we may apply the methods based on an equation of slate 10 a system defined
in this way (see Olaplcr 8). However. k.nowledge of the Henry constants (see Chapler 5.
Section 5.9) often provides a simple solut;on 10 the problem at hand.
First wc shall consider the case of a binary system: a permanent gas (component 1) and
a !;(llvenl (component 2).
The Henry constanl of the gas in the solvent is defined by the equation:

?lIn'" lim
.,.....0
(f,')
Xl
(5.86)

It depends on the identity of the gas.. of the solvent. and on the temperature.
At moderate pressure (a few dozen bar). the solubility of the gas in the liquid phase is
weak. such that we may write:
(6.30)

While still al moderate pressure. the fugacity of the gas in the vapor phase is dose 10 ils
partial pressure:
(6.31)

The equilibrium condition therefore leads to the following upression for solubility of
the gas in the liquid phase:
Py,
x,.--
"IP-
(6.32)

So. as a first approximation. thc solubility of a gas in a liquid solvent is proponiollalto


its partial pressure. This is the Henry law statemenl. and the range of composition and
pressure for which this law is reasonably complied with is often designated as the range of
application of the Henry law. This range varies according to the nature of the gas. If it is at
a temperature that is clearly higher than its critical temperature. the approximation repre-
sented by Equation 6.31 is well verified. Such is the case for solutions of nitrogen and
methane for example. and for pressures up to 100 bar.
The previous equations show that the Henry constant plays the role of a corrected
vapor pressure. especially in order to take into account the non-ideality (in the symmetric
con\'ention sense) of the mixture.
We can apply these equations to solutions dilutcd with a "subcritical" component. and
express the equilibrium condition either with the equation;

(6.4)

or by using the Henry constant:

(6.33)

and thereby more casily relate the Henry constant to vapor pressure, activity coefficient at
infinite dilution. fugacity eocfflCienl5 at saturation, and the Poynting correction.
206 6. Mixwl'l'S: liquld.v"fl'lX Equilibria

If the system io question has several gas solutes. we call say thaI as long as their solubil·
ity remains low. their interactions are negligible. and Equation 6.32 is applicable 10 each
one of them.
On the Olher hand. if lhe "solvent" is a mixture. the Henry constants for each of lhe
solutes depend on the composition of the solvent.

REFERENCES

Abbon MM (1986). Low pressure pha"" equilibria: mca,urcmenl ofVLE. Fluul Phme Equilibria, 29.
193·207.
Agarwal KK. Li Y·K. Nghiem LX. Coombe DA (1991) Muhiphase multicomponenl ;SoentlJalpic nash
calculation.). C"",.JiDn Prrroku", T«/rnology. 30. No. 3. 69-15.
A_linea.. 1., Bog<lanic G. Vidal J (1979) A venat;'" algorithm for calculating ,-apour-liquid cquili-
bria. 1'7,,/<1 Phtu, Equilibri... 3. 213-290.
B~ker LE. Luks KD (19711) Critical poim and Ylur.llion pressure cakulations for multicomJXlncnt
systems. P3~r preM:ntoo al the JJ rd SPE mUlinG, Houston. Oclobc:r 1978. ref. SPE 7478.
Baker LE. Pierce AC. Luks KD (1982) Gibbs energy analysis of phase equilibria. SPE Journ..t,
Oclober.731·741.
Boissona~ (1939) lid". CM",. Acra. 22. 541.
Deite,." UK. Schneider GM (1\186) High pressure phase: equilibria: cxpcrimemal methodli. HuM
Pha,c Equilibria.29. 145-160.
Gmehling J. Onken U (1978) Vapor-liquid equilibrium data colleclion. Chemi,try Da/ll Serin.
De<:hcma.
Heidemann RA. Khalil AM (1980)Thc: calculation of crhical poin",- AlelrE ).• 26. 7@·779.
Holste Jc. Hall KR. Eubank PT. Manh KN (1986) High prL"SSure PVT measurements. Fluid P1uJM
Equilibria. 29. 161 .176-
Hougen OA. Watson KM. Ragatlt RA (1959) Clremieal Pf'()(;fi$ Principln. Wiley &1 1IOflS. Ed.
Kehiaian tl/munati""at Da,a Seric. Scr. A. 1lIermodynamie propenies of n<MI-reaet;ng binary sys.
lems of organic substances. TheTexa. A&1M Univenity.
Kreglc...",ki A (1984) Equilibrium P'OMnies QI Fluids "nd Fluid MiJt:'u~. TexM A&M Univen;ty
Pr"", College Slat;<MI. Texas.
Marslt KN (1989) New methods for ""por liquid c:quilibria measurements. Fluill PIrU$e EquilibrilJ. S2.
16\1-184.
Michelsen ML (1980) Calculalion of phase envelOJ'l'S and critical poinu for multicomponent mixtu·
rL.... Fluid Plrase F.qui/ibri... 4. 1-10.
Michelsen ML (l9ll2a)Thc isothermal nash problem. Part I. Stability. Auid Phase Equilibria.9. 1.19.
Michelsen ML (l9H2b) The ;sothermal nash problem. Part II. Phase split ealculalion. Fluid Phase
E./"i1ibriu. 9. 21-40.
Michelsen ML ( 1985) Simplified nash ealculations for cubic c:quation. "f stale. 111I1. ""g. ehe",. 1'",,,.
De$. Dey.. 2S. 184·188.
Nghiem LX. Li Y·K. Heidemann KA (19SS) Application of Ihe langent pla"", criterion to salUtlIt;Qtl
pressure and tcn'peralure compulatio..... Fluid !'Iome Equilibria 21.30-«1.
6. Mi~tures: Liquid·V..,- EquWbri.. 207

Olsuki H. Williams Fe (1953) Eff«l of pressure on vapor.liquid C<luilibria for 1M system "lhyl alco-
hol watcr. Chl'm. En/? Prog'I'~:S)"'lrposiunr &ril's.49 (6). 55~7.
Rachford HH Jr. Rice 10 (1952) J. Pt,roJ. T«/HWI.. 4. (I). 19: (2). 3.
Rcnon t1. Assclineau 1-. Collen G. Raimbaull C (1971) Cdltul sur a,dilldll'ur da #q"ilibra liquid,.·
"afl<"'l ~ liquid" liquid". £ditions Tcchnip. Paris.
Rowlinson JS, Swinlon FL (1982) Liquid ami Liquid Mixflll'tt J«l edilion. BUllcrwonh. Lor>don_
Vidal J (1974) Th",modynamiqll"- /..Q milhooa lIppliquhl all 'liffinap CI au gini" cllimiqu". I!di·
tionsTechnip. Paris.
WIChterle 1. Linck J. Hala E (1973-8S) Vllpt>r-J.lquid Equilibrium BibliQlJraphy. EIse~icr. Amslerdam.
WIChterle I. Linck J. Wagner Z. K"hiaian HV (1993) V"por-Liquid Equilibrium Hibliogrophk DUIII
BIlSt!. Eldala. S"'IlL., Montreuil. Franc;:.
I
7 Deviations from Ideality
in the Liquid Phase

In the preceding ChaplC1'li we have shown thai we can estimate the liquid-vapor equilibria
81 low pressure and the properties of a mixture in the liquid phase by using the following
steps:
• Calculate the properties of each oomponent in the reference state.
• Call:ulate the properties of the mixture in the ideal state.
• Calculate the excess quantities.
The first of these steps involves the application of the methods presented in Chapters 2
and 3. However. we may run inlo some difficulties. A liquid mixture may COIllain oompo-
nents that. if pure. would be in the vapor state or ()OSSibly in the supercriticaJ stale. In par-
ticular. such is the case if it is in equilibrium with a vapor phase (meaning at its bubble
point). Under these conditions and for the lightest of its oomponenl5, the reference Slate is
not stable and corresponds to a superheated liquid. To estimate Ihe properties of sueh a
stale requires simplifying hypotheses. These hypotheses are plausible as long as we are at a
temperature significantly below the c:ritieal temperature of the componenl in question. We
consider the molar volume equal to the molar volume at saturation. The same is true for
the enthalpy. Finally. for fugacily we will use the Poynting oorrt:etion even if the pressure is
less than the vapor pressure. Near the critical point, this p~dure becomes questionable
and. at a temperature higher than Ihe eriticaltemperature. it may not be applied because
Ihe properties at saturalioo do not exist.
This estimation process for liquid phase properties is therefore only viable if tlte lem-
pn1Illln III de_rty lower tfl.an the c:ridc.llempe...tu", of .lIlhe compoMnl$. We will IIlie
Ihh hypolhftls.
The second step involves the mixing properties that characterize: the ideal solution.
The volume of mixing of the ideal mixture is zero as is the heat capacity of mixing
or the enthalpy of mixing. This is nOltrue for the entropy or the Gibbs energy of mix-
mg.
The last step involves experimental data.oorrelation.or even prediction of ex~ quan-
tities on the basis of "models~. The goal of this chapter is to introduce some ooncrete
examples of deviation from ideality. primarily emphasizing the dfect5 that these devia·
lions have in terms of liquid-vapor equilibrium. As we are already familiar with the essen·
210 7. ()evj~riQm from ldealiry in the liquid Ph.I5e

lial role of act;vity codficientSo. we shall introduce the models that arc most often applied
to their correlation and prediction.

7.1 EXCESS QUANTITIES

7.1.1 heess Volume. Excess Heat Capacity

These quantities arc oflen neglected in calculations. It is true thallhc excess volume (the
dilatation or contraction upon mildng) is generally very low. Figure 7.1 [Berro. 1986] shows
the variation of this quantity with the composition for the ethanoill-heplane m1Jllllre. NOle
thaI the maximum value of exccss quantity is OJ cm J . mol~l. or around 0.5% in relalive
Yalue. The precision with lI>'hich the properties in the reference stale and the ideal solution
are evaluated is usually much lower. Therefore. the excess volume may rightly be neg-
lected.A re\';ew of the experimental dala was done by Battino 11971] and more recemly by
Handa and Benson 11979].

0.6

,-
I 0.'

1
•>

0.2

0.5 x,

Flpre 7.1 Mi;ting \"Olulnc oflhc ethanol (I) ,,·heptane (2) s)"Stem.
(Ekrro.l986].
211

By applying Equation 5.78. we can conclude that the acllvlIy ooefficicnlS under
these conditions aTC practically independent of pressure. Indeed, we shall see Ihal the
models relating to excess Gibb!; energy retain only composition and Icmpel1lture as vari·
able.
As for excess heal capacity lhal determines the influence of temperature on lhe heal of
mixing. it is also commonly ncgl=ted. Figure 7.21Cos18s and Pallerwn, 198.'i] for Ihe ben-
zene n-decane mixture shows that it may. however. reach -4 J . K-l . mol-I. a value tllal we
can compare to the benltcnc heat capacity at the same temperature, 137 Jlmol.'n faci. we
have access [0 many experimental measurements concerning this propeny. but the models
thai arc applied to the deviation from ideality cannot represent C:lCCSS Gibbs energy. heal
of mixing. and excess heat capacity all at lhe same time.

- -,
;
~
;

-" -.
~

0,5 .l",

I'1pn' 7.2 E~ccss molar helll cupacilia of lhe benzene (1)


II-1.kxane (2) syslem ICoslas and Pauerson. 19851.

However. this is Dquantity thaI seems panicularly sensilive to the structure of a solution
and to the molecular interactions tllal occur upon mixing. The example of Ihe 1.4 dioxan
cydohexanc system is given in Figure 7.3 [Trejo tH uf.• 1991}. The excess quantity is low in
relative value. but the shape of its variation with the composition reveats the complexity of
the system and representS a challenge to any model that is not based on a real understand-
ing of the phenomena at work.
o

".,
,
~ " .•
~

"..
" "., "'- J-0

".,
-1.0
V
0' "
""'1"1' 703 Exccc$5 molar heal capacities for the 1-4-dioxan (1)
cydobcXIlllC (2) $Y!'!cm jTrejo <:1 al.. l\1911.

7.1.2 Heat of Mixing

It is very clear thallhis quantity is part of enthalpic balances. It also enters into the calcu-
lation of separalion pr~ by both enthalpic balance al each stage and by the rae! that
partial excess molar enlhalpies determine the variation of the aC1lvit)' coefficients with
temperalure, as Equalion 5.77 shows;

<3 (In )'j») lit


.-.., (s.n)
(
aT I'J'V"I RT
For example. it has been shown thai omitting Ihis quam!t)' from the calculation of the
cyclohexanol cydohcxanone miXIUTe distillation yields a product of unacceptable purity or
a proouctioll that is diminished by 30% rZudkevitch, 19781.
The order of magnitude and the sign of the heat of mixing are variable. For binary
hydrocaroon system!;. lhe influenee or $trueture has been the subject or a detailed sludy
[see Abdoul ef 01.• 1991. for tIIamplej. Generally moderale and posilive (Fig. 7.4). the quan-
lily is very sensitive 10 lemperature when lhe millture components have very difrerent
chain lengths (Fig. 7.S). Furthcnnore. il may reach several kilojoules in Ihe case of specific
interactions. It may al!iO happen thaI a s)'Stem. seemingly ideal from the point of view of
Gibbs energy. has a high heal of mixing. Such i$ the ease with water dimethylformamide
milltures. As with heat Capacily. but generally 10 a lesser degree. its variation Wilh the com-
213

"""
900 8.

,.
(J·moI-')

"
60 b.

'"

0,5 ;II (1Hle1<arMl)

f11"~ 1'" Exce5lI ",nlhalpks fur hyd.-.x:a.bon mixlUrn


.. benzene" ".hepla"", (0); .. n-undcca"": ee):
.. 1I-l"'nUKlecane (.).
b. n-henne .. ,,-<)Clane: ("'):" ,,·decant: (e);n-dodecanc (0);
.. II-hcudecane (*).
214

o 0.' ;II (hexane)

t-IflU~
1.5 Variation of cxcc:ss enthalpy of Ihe n-hexane n-hcxadccanc
s~lcm ....ith temperature.
298.16 ( .. ): 313.15 (0): 324.15 (e): 333.15 (¢): 349.15 (4).

position may be the sign of complex molecular interactions. This is lhe case wilh the waler
cthanol system Wig. 7.6. L.'rkin ~f 111.. 19151 for which dC\'iations from the ideal behavior
may be interpreted by the rupture and recombination of hydrogen bonds.
The model for heat of mixing is generally paired with that of excess Gibbs energy as
soon as the model applied 10 this second property lakes into OC(:Ollnl the influence of tern-
pc:mlLirc. However. il must be emphasized lhal the change of excess Gibbs energy wilh
composition is generally simpler than that of heal of mixing. and priority is most oflen
given [a the calculation of aClivity coefficients. Hcnce. the models are oflen less accurate
whcn applied to the heal of mixing. So. in the case of lhe above-mentioned waler elhanol
mixture. exeess Gibbs energy is moderate and its varinlion with composition leaves nOlh-
ing to be predicted from the shape of lhe /rf:(.r) curves.

7.1.3 Excess Gibbs Energy and Activity Coefficients

Generally. lhe models involve excess Gibbs cnergy. but Ihe practical impacl of devialions
from ideality on phase equilibria is evaluated in terms of aetivityeucfflcicms. We have seen
thaI allow pressure the liquid-vapor equilibrium coefficient. ratio of lhe mole fractions in
both phases. is calculaled using Equotion 6.5:

I
215

200
, 343.15 K
1 0

•"<
-200

o 0.' Cl.4 0.6 0.6 ,


>r{eIhanoI}

figure 7.6 Variation of llle excess enthalpy for too etballQI (I)
....ater (2) S)'Slem with temperJI[urc {Larkin t/ al.• 19751.

allow pressure (6.5)

where P/' represents the vapor pressure. Pthe pressure. and Yi the IIctivity coefficient in the
liquid phase. It is therefore in tcnns of Iht activity coefficients th8t we shall provide II few
examples. The activity ooeflicicllts arc composition dependent. and as we have already
mentioned. it is in II dilute medium thllt the behavior of II component usually differs Ihe
mOSt from its properties in an ideal solution. The aetivit)' coefficients al infinite dilution
therefore represenl. in II way, II Mscal c of non·idcality-. Table 7. t concerns h)'drocarbon
mixtures. II shows that mixtures containing paraffins and aromatics arc unwaveringly non
ideal. In a dilull: solution of benzene. the volatility of heplane is increased by about 70%.
such that despite the difference in boiling temperature (llO"C for benzene. lllO"C for hep-
tane). the separalion by simple distillation is impossible. as predicted by the "pinch" zone
seen in the liquid·...apor equilibrium diagram of this mixture (Fig. 7.7). In any case. such
de ...iations cannot be neglected. Howe ...er. if the molar ...olumes are nol appreciably differ-
ent. hydrocarbon mixtures of the SlIme family may be considercd ideal.
216 7. lJcvi.Jrions from iOOality in the liquid Ph.-

T.b~7.1
ACliv;ly roefflcienls at infinite dilution in hydrocarbon mixtures

Components
I 2
8
(oq
y; y;
Hexane Benzene 68 1.7 I.'
Heptane Benzene OJ 1.7 1.35
Heptane Benzene: OJ 1.6 13
Hexane Toluene 24.8 1.8 1.6
Toluene

'"'81"
Heptane IA 13
Cyc:lohexane Bcfl8ne IA
Cyclohe.une Toluene "
13' 13'

'00 - , - - - - - - - - - - - - ,

0.75
, ,
, ,
, ,
, ,
, ,
, ,
, ,
,
,,

,-F-'----r-----,--,------1
" "

Figure 7.7 Liquid·,,,"por equilibrium diagram of the benzene (I).


,,-he plane .yo.ern a1 almospheric pressure.
217

The mixtures containing both apolar compounds (hydrocarbons) and polar compounds
show deviations from ideality of an entirely different order of magnitude. As an example.
Table 72 lists activity coefficients at infinite dilution rOT heptane and ben1.cne in some
polar oompounds..

T. . . 7.l
Activity ooefTlcicllts ~t infinite dilution for heptane (I)
and Jx,n~1l<' (2) in polar compounds

Soh'cnl
,(Oel 1;
,
("C)
".6
A~lon"
Methanol '"'" "
6A 31

.,
J<J '.2
S.,
Ethanol
'" IJ
••
Dimethylformamidc
Dimethylsulfoxide "" "
121 "" J2
J.l
ElhylcrIC glycol
" 15"
"
We observe lhal in a dilute medium. the volatility of a hydrocarbon is considerably
modified and that the polar compound acts selectively as the actiVity coefficient is VCr)'
sensitive to the nature of Ihe hydrocarbon. As such. in dimclhylformamide lhe relalive
volatility of heptane and of benzene is multiplied by the IlCtillity coefficients ratio. 21/1.4.
In an extractille distillation performed in the presence of this soillent. heptane will b<: dim"
inated at the head of the column although its ooiling temperature is woe low~r than that
of b<:nzene.
The elellated lIalues for the actillity coefficients generally gh'e rise to partial miscibility
in tbe liquid phase. This can be observed for heptane in methanol. dimethylformamide.
dimethylsulfoxide. and cthylen~ glycol. The aromatic hydrocarbon miscibility in these sol-
lIents is.. if notlotal. at least higher. and the liquid liquid extraction purification processes
rely on this selectillity (sec Chapler 9).
The examples of delliatioll from the ideal mixture thaI we halle just discussed yield
Mposilille" delliations.. The aClillity coefficients are greatcr than one and the excess G,bbs
energy is positillc. If it exists.. the a..:eotrope phenomenon is observed by a pressure maxi-
mum (or II temperature minimum). Such is most frequently the case. at least for "non e1cc·
trolyte" mixtures.. We shall see. howe\·er.thal the molecular 1I0lume differences cause neg-
ative deviations that may be IIcry large in the case of polymer solutions..
At the molecular 11'111'1. the mixture of two polM compounds is accompanied by the rup-
lure of dipolar interactions b<:twccn idemical molecules and the reestablishment of such
interactions between different molecules.. [t is difficult to predict the resulting sign and
magnitud~ of their deviations from ideality.
1,-

7 ,2 E-.

- Uul YU',lill

,
= -::;: -
,,1f1
t
r~ p ~.

rial
'1. 1

I: '.h t r·

'. ~ 1.
u

.RT ~
n":l'-:=
~ If
'.1'
- I
'.
._
,,-,
II'·

17."
~ , t

a
,.,
'1'11 ~

h It
7 - ."Ii

"''- ,~_ .
'

lab!le.:: ,""
acellY~Otf rit, l' mJOWlme

1 'I

,,
2 - I
~

,. .'
--
,J
l-
20 -
I'
~
,. J

~
::II I'
en
, ,. "
w 5
!

0·25 '0.5
" I

riu:m

rial
221

Estimation of Experimental Precision


Coherence Test

In the preceding cumple we should, ;n faet, have compared the calculated deviations.
after optimization. 10 the experimental uncertainties. These bear on temperature (61'). the
compositions (&). and pre$ure (61'). Calculating the pressure fOf" the values of the com-
position and temperalUre taken as ~lrue", we may relate the relative uncertainties at these
quantities to the pressure by defining a "resulting uncertainty" t!J".

Iipl = O/il ~ (~~r.sTl + ( : ) ; {jr (7.4)

and the function Ihal we minimize is defined by:

where (75)

where "c.p and "par respectively denote the number of experimental points (except tile
pure substances) and the number of parametcl'lI (equal to one in the previous example).
This average quadratic deviation 0,..
according to it$ definition, must be close to unity ill
order for the correlation to be deemed s:lti$factory. If $uch i$ nOi the case. we may fi~t
blame the model. and con$ider it unable 10 rcprel;Cnt the system in question.
In practice. we apply the expression proposed by Redlich·Kister I194llJ for the excess
Gibbs energy:

(7.6)

At first glance. this expression is perfedly flexible. It will be successively truncated after
the first. then the second. then the third term. each time optimizing the parameters (mini·
mV-lItiOIl relatillg to the Co variables. then Co. C 1, etc.). The improvement can be continu-
ally monitored by evaluating the decrease in the average quadratic deviation defined by
Equation 7.5. When this improvement is no longer substantial. we can say that the residual
deviation is indeed the result of experimental uncenainty.lf it differs significantly from the
value of one. we can say that these uncenainties were ullderestimated. Of. more rarely.
overestimated.
Of course. ill the case where we proceed with such an analysis, we mustlKCOunt for the
imperfection of the vapor phase and Ihe Poynting correction, and exprCS!l the equilibrium
coefficienls in the general form 6.4:

(6.4)

the fugacity coefficients being calculated. at low pressure. using the virial equation of state
trunc:ated after the second tcon. The virial coefficients will be preferably estimated from
experimental data. or. if none are available. from a predictive correlation such as that from
Tsonopoulos (see Chapler 5).ln this case. the calculation of the binary coefficient 8 1,2 may
introduce a -bias- into the data correlation.
m 7. Dt'V~,tior>j (TOm Irl&Iliry in rhe Liquid Phd..,

Finally.....e note thaI Ihis method may only be applied when the Jluml>er of experimen-
tal points is large compared 10 the number of adjusted parameters. Olher excess Gibbs
energy expressions have been proposed. for example. based on the use of orthogonal poly-
nomials [Christiansen and Fredcnsluncl.197S; Klaus and van Ness, 1967].
When we usc "complete" dllla (Ihal is to say thaI we have available temperature. pres-
sure. and the composition of the two phases). we may then determine tlleir coherence. For
this we define three objeaivc functions:

It is understood that lhe "resulting" uncertainly for the compositions in the vapor phase
6y is estimated in lhe same way as the one relative to pressure !J.P. The definition for
the two lasl objective functions oomCJl back to subdi\'iding the data into two ~incomplele"
sub·sets. Through minimization of each one of thesc three objective funclions we deler·
mine the parameters of the model. The results mUSt be the SlIme wilhin the uncertainly
inlerval or these parameters. Table 7.5 shows this approach INeau. 19791 applied 10 a
melhanoill-propanol system [Berro 1'1 ul.. 19751. In lhis case, lhe Redlich·KiSler equation
is rcwriuen as:

and we erreclivcly observe the coherence of the PMameters. We also note thatlhe results
rrom incomplele TI'x or complete TPxy data are equivalent as far as precision obtained
rOT lhe parameters. [t is nOl the SlIme for Txy data. which contain less "informalion".

T.ble 7..5
Correlation of the equilibrium data of the methanol ".pr"""nol 5)"Stcm I&rro. 19751_
Data pl"OCC'~ing and roherence nteasurcmenl

Data Type TPxy Tf'.: T"


Objective F'unctio" SQ, SQ, SQ,
C, 0.0647:to 0.001 7 0.0639:to 0.0013 0.0645:to 0.0034
C, 0.0081 :t 0.0006 0.0082:t 0.0007 0.0063:t 0.0016
C, 0.002 9 :t 0.0007 0.0032:t 0.0007 0.0036,. 0.0016
223

As we have already noted (see Chapler 6. Seclion 6.3.3),lhe oohcrence tests may usc only
data al low pressure. Under these eonditions only can Ihe vapor phase be strictly repre-
sented by a vinal equation of Slate truncated afu:r Ihe seoond term. In addition, thCS<' tests
8rc applicable only to binary mixtures for whkh we have numerous data thaI covers the
entire oomposilion interval, and whl)Sl,l uncertainty has been estimated. ThC!ie items were
studied by E. Neau [1979). P~neloux Itl pl. [1975. 1976. 1990].and Neau and P~neloux 119811.

7.3 INFLUENCE QFVARYING MQLARVQLUME:


THE COMBINATORIAL TERM

Up until this point. we anributcd Ihe deviations from ideality to molecular imcraclions.
and it is just Ihis mailer thai will intervene in the models thai are to be discussed fUrlher
on, and thai are commonly applied.
However. we must emphasize that in a miJrlure contalninl compoulMfs of very different
11I0'" volumn. e~a if'theH compounds are of a simi"r dJemieU ulure, we lIIIIy obse"'e
non-lIeJIiJibIe devialions from idnlily. Such is lhe case for SOlulions of monomers wilhin
its polymer. or for example. polyethylene in parafl'inic hydrocarbons.
Acrordilll to Flory 11942:) and Husgim 11941. 1942:1. these deviaoom from idealily are of
mlropk oriJln. and correspond 10 the possibililies of distribution of the polymer molecules
H
in a lridimensionallanice.The term "oombinalorial refers to these types of deviations.
U we consider a binary system composed of a high molecular weighl compound (the
Hpolymer-). lhat can be represenled by a chain containinl p segment$. with each segmenl
occupying one node of the lanice (Fig. 7.9). as well as a low molecular weight compound
whose molecule occupies only one Sill'. a mixture containing N 1 molecules of this second
compound and N1 molecules of the polymer will occupy a lattice of N l + pN1 Siles.
We will assess the various possible arrangemems. To do lhi!;. we first look at lhc firsl
segmenl of the firsl polymer molecule: lhere are N I + pN2 possibilities. For Ihe St,.'(:Ond seg·
ment. we must accounl for lhe number of neighboring siles 2. which we call the coordina-
tion number of the lanice.The third segment may occupy only t. - I sites. one of thc bor-
dering sites being occupied by the second segment. and il is the same for subsequenl leg-
menlS up 10 the lasl sill' of lhe first polymer molecule. This firsl molecule Iherefore has:
PI ., (N I + pNJt.(t. - 1)p"2 dislinct configurations
If we lake Ihe k'~ polymer molecule. we only have (N I + pNJ - (k- I)p vacant sites. and
we will consider that the number of configurations for Ihe placemenl of each segmenl has
been reduced in proportion with Ihe remaining sites. We therdore have:

or in other words:
For the N~ polymer mol~ules. the total number of possible configurations Qu •is equal
to the product or the terms so determined. divided by N2!.as the N1 polymer molecules are
indistinguishable. The molecules of the low molecular weight component that occupy only
onc lauice site are placed on the remaining sites without introducing new configurations
since they are themselves indistinguishable. Therefore. in total. for the mixture under
examination we have:
I N,
Quo = N ,. I n htPt

We must now compare thcse configurations to those evaluated for the pure substances.
QI.I is equal to one. and Q2.l is determined using the same equation as for Quo' with Nt = 0
of course.
From these numbers or l;onfigur3tions and according to the results of statistical thermo-
dynamics. we can l;alculate the entropy of mi~ing:

SM" k(ln QI.2 -In Qu -In Q1.2)


where k is the Bollzmann constant. We replace Ql.2' QI.l' Q u with their values and apply
the Stirling approximation:
InN!"'NlnN-N
10 arrive at the equation:

• •ure 7.9 SchcmatH: ",!""""malion or.he Flory I'Cli<:ular model.


7. DeviafK>m from IdNlity in IN> liquid I'h.J5,e 225

As each site has the ~me volume. the ratio of molecular volumes vI is equal to p. and
we obtain the volumetric fraC1ions;

,od

We thus arrive at the expression for the ennopy of mixing for one mole:
,"
Ii" "-(XI In <PI + '(2 1n <P;z.> (1.7)

This expression differs from the entropy of mixing of the ideal solution, which is written
~,

such thai excess entropy is equal to:

"-"'-
R
(xlln-'~x, (7.8)

where:

To this entropy term. which we shall generalize for a mixture of II components. corre-
sponds a component of exct.'SS Gibbs energy:

t: F. ~
g coonbiooJol<>ri.lI1 = - Ts . '" RT ~xlln -
.pi ~_ v;
= RT .::.rlln - (7.9)
X; II

This term is always negative. By applying Equation 5.75:

(5.75)

we get the following expression for the activity coefficients (which are always less thlln I):

(7.10)

I n particular. at infinite dilution in a binary mixture:

(7.11)

since the ratio v;lv; is equal to p. we ultimately have:

1 1
In ri",ln - + 1-- Inr;-lnp+l-p
P P
226

As an example. table 7.6 shows the values lhal these activity coefficients may take as a
function of the molar volume ratio:

T.b.. 1.6
Acti"il)' eoefrlcknlS at infinite dilution
calculated by applialion of the Flory theory
(p .. vifu·,)

, '; ri
,
2 0.82
0.44
0.74
0.09
1.2 IO-J
10 0.245
100 2.7 10-1 1O-~

1IlOO 2.7 10-l 10-0 ;1

II goes without saying thai we can only take these results as a qualitative indication of
the large deYialions from ideality caused by Ihe differences in molar volume. The hypothe-
ses on which the model is based (analogous lanice for a crystalline system. linear mole-
cules. clc.) arc debatable.
In order 10 aCCOUll1 for mol«uJar form. it has been proposed 10 characterize them both
by their volume and by their external surface. If we have linear molecules. these two prop.-
erties remain proportional when the chain length increases. for example. in the n-paraJftns.
[1 is not the same. if due to CYC[iZalion or branching the molecules have a more compact
form. or even globular. If we designate the external surface of lhe molecule of component
i as q;. and the corresponding surface fraction as 8;:

i'<""'-
8. =
, L xJqi
(7.12)

J
the model proposed by Stavemtann [1950] leads to the equation:

g~bdlalONl = la[LX, In :; + i ~>/;Xi In ~] (7.13)

....here we also re<:ognize the term proposed by Aory. The Stavermann model was utilized
in the UNIQUAC lind UNIFAC methods. which we shall introduce later.
To illustrate the deviations (rom ideality for polymer solutions. we must also take into
account the fact that the proportiOn of "free volume" (meaning volume not occupied by
the molecule itself) is generally smaller for 1I polymer than for a solvent (see Chapter II).
In any even!. we may not overlook the role played by molecular interactions and the
enthalpic component. A simple means of accounting for them consists of expressing the
enthalpy of mixing using the equation:
227

where X. called the "interchange parameter", is empirical. and must be determined from
experimental dala. In this case. for a binary mixture the excess Gibbs energy is:

8" 4>1 4>l


- '" XI In - + "lin - + [(XI + PX2)4>I'Pl (7.14)
RT XI x~

In tcOndus.ion. the lenn "enlrop"''' or "wmblmuorial" that we h8VC jusl IntroduCfll is


only one oomponent of non-ideality.
Molecular interactions playa role in the energy balance accompanying the mixing
proces.... They exert 11 poorly understood but undeniable innuence on the surroundings at a
short distance from the interaction focal point (molecule or group). The models thaI we
shall now consider are focused on theif oomribution.

7.4 THE CONCEPT OF LOCAL COMPOSITION

The nOlion of"local composition" was introduced by GM. Wilson 119641.11 is the source of
the models deemed best for the correlation and prediction of deviation from ideality. They
include the Wilson equation. the NRTL model. and UNIQUAC
If we look at a binary mixture and first examine the system formed by the components
before mixing. and then after mixing (Fig. 7.10). we note that:
• Before mixing. eaeh molecule is surrounded by similar molecules. and exhibits with
each one of them an interaction energy £1.1 for the firsl component and ~.l for the
st-eond. The numbers of closest neighbors. II and l2' are called the coordination num·
bers:
• Arter mixing. ti molecules are distributed around each molecule of component I lind
lhe composition of this environment depends of eourse on the overall composition.
but need not be idenlical to it. The molecules of a polar componenl may have the ten·
dency to group due to the effect of orientation forces. and in this way exclude the mol-
ecuJcs from an apolar component from their neighboring area. This tendency may
continue until demuing. We denole the mole fraclions of components I and 2.x2.I and
XI.\, respectively. around a molecule of component I. The description of a eenler of
aUraction formed by II molecule of componenl 2 will be similar and will introduce the
quantities ti,xl.l' and xu' As for the molecular interactions in the mixture. they arc
of three lypeS according to the nature of lhe centers of allraction: £1.1' tu when the
centers are lhe same. and ell '" l:.z.1 if they arc different. Of course. the valul;'S inlro-
duced here correspond 10 averdgcs. and should only be considered 3.$ the pamml;'ters
of II model.
On these bases. we shall establish the energy balance of the mixture with n l molecules
of component I with 111 molecules of component 2.
Beginning Wilh pure component l. in order to extract one molecule. it is necessary to
fumish an energy equal to t 1f\.1' and its introduction into the mixture trallslates illto an
interaction of ti(xl.l£l.I + x1.l€z.t) or a variation equal to tleu -1:1(x1,1el.l + X1.I!:1J)'
Similarly. for a molecule of component 2. the transfer is accompanied by II varia lion in
22. 7. Deviations from JdNIiIy i" 100 Liqukl Ph.•..,

energy equal to ~z£u - z; (XI,lE lJ + xuE:zJ)' For one mole of the mixture the IOlal energy
variation. using 1{for Avogadro's number. is therefore writlen:

uU '" ~ 11111 z I (.,1 - z; (.1 1•1E1.I + .12,1 £z.1)J + 1111Zz tU - zi (x l,2 GoJ + Xu£.z.J J1
where the term 112 is introduced since otherwise each interaction is counted twice.
Such an clrprcssion contains 100 many inaccessible quantities to be truJy useful. We
must introduce approximations and propose a way to evaluate local compositions. We also
ha\'c 10 move from energy balance to excess Gibbs energy. Each of these steps will eslaD-
lish an empirical model whose valut will dCpl.'nd on the phy:;ical meaning and on its pre-
dictive power.
Finlily. we will admit thaI the degrees of coordination arc not modified by the operation
of mixing. Furthermore. around a given molecule. the sum of Ihe local compositions is
equal to I:
.'
~1 '" ~i>
.
and:

,. ., • •
f'
• •
,
,, •
,
,, • '"
,
,
•. ~. • '..... ~

, ....
••• "
•,, , •••
," , '., ~

. .....," .... "


,
oW.

,

~ 7.11 Concepl of local rompo!iiliOfl1.


245 t
x, -Xl ,,0.5: Xu = (; .X:., - (; .x,.2- (; .xu - (;.

such Ihat for one mole of mixture. the expression for the exeess internal energy. or 10lernal
energy of mixing. bewmes:

II C '" ,,/14 : -~ 'J(. [~IxtXl.t(~1 - c u ) + ~2x2.r 1.2(f:l.l - eu) I (7.IS)

Note that only the differences belween Ihe molecular interactions, ~I - f: 1.1· £l.l - eu
appear in this expression.

p'
229

7.4.1 The lattice Model

In order to further simplify this internal energy of mixing. we conCle(\e Ihal the compo-
nents. whether in the pure stale or in the mixture. have identical molecular volumes. Each
molecule occupies onc segment in the ordered lattice as the one pictured in Rgllre 7.9
since Ihis lattice is unchanged upon mixing.
It is also aca:ptoblc thai lhe local compositions are identical to the global compositions.
Equation 7.15 may be wrinen as:

To get excess Helmholl1: cnergy. we apply the Gibbs-Helmholtz equation:

"
a-
RT
,,-T , . -
R
and thus ," It ,,' (')
1iT= 1. lid T +ronSI.
'.
If we admit lhal E;,j interactions (and therefore the internal energy of mixing) arc nOI
temperature dependent, we obtain:
aC liE
- < -+conSI.
RT RT
The integration COfISlanl is obtained by considering lhe limit l\$ T ...... _. The excess
Helmholtz energy is thcn equal to exeess cntropy, which is "{eTO due to the hypolhesis
established for lhe local mole fractions (the mixture is "random"). Therefore:

aE lIE ?{l. A I .2
RT = RT = - 2 RT (2£2.1 - £U - £u>x t x2 = liT ,l"lxzl
Accounting for the lallice hypothesis lhat is identical for the pure substance as well as
for the mixture. the excess volume is nult. and we cnd up with the same expression for
exceu Gibbs energy:

g
, ", ( Au
RT=-2RT 2Cz.I-e,.I-tuJxIX~=RTXI,l"2

The term A 1.2' related to the molecular intcra<;,tions. may be dl:termined rrom thc liquid·
vaporeqllilibrillm uperimental data. as we have seen previously (Section 72. Example 7.1).

7.4.2 The Quasi Chemical Model

Guggenheim [19521 introdu<;,ed the "quasi <;,hcmical" model. and its main principles have
been presenled by Prausni12 tlll/. (19861. This model may be considered a special ease of
the models for local mole fractions lsee Panayiotou and Ve.... 1980; Ve..., 19861. The
230

Clitablishment of mol«ular interactions upon mixing is expressed as a re\'crsiblc chemical


transformation:
[I-II'" [2-2J -+ 2[1-21
If "OJ is the number of m:ighboring ij in the mixture containing n l molecules of CQmpo-
nelll 1. and lIZ molecules of componenll. then Ihe equilibrium condition call be expressed by:
,
IIi,;!

/11.1"U

The equilibrium constant K is related 10 the energies of interaction G.; by the equation:

K1,2" 4 cxp ( ti -Eu)


2E U -E t J

Considering the material blllanccs acting on each romponent. we may calculate the val-
ues for the neighboring"lJ and the local mole fractions.
This model as well as several of ils variants thai have been published. are undoubtedly
less clllpiricalthan the Wilson. NRTL. or UNIQUAC models. However. it introduces cer-
tain practical disadvanlagCli Ihal have limited illi IISC. FiBII)'. it has only onc parameter (the
equilibrium constant) per binary. which detracts from its ncxibility. SeCQndly. its applica-
tion 10 a mixture .....ith It components necessitates solving a sr.;tem of equations of the sec-
ond order. ""hieh is less desirable from the point ofvicw of efficient calculation. It has been
applicd in group contribution interpretations by Kehiaian [1983. 19881. and by Panayiotou
and Vera [19801 and High and Danner [1990lto dcscribe poJ)'mcr solutions, as .....e shall sec
lateran (Chapter II).

7.4.3 General Remarks

The most commonly applied models. regular solutions, the Wilson model. NRTL UNl-
QUAe. llnd UNIFAC may be gencratcd from the local CQmposition concept. such as
expressed in Equation 7.15:

M I
It'; '" 11 '" -2 ~\':lll.fI"'2.I(~1 -£1.1) + :l"'l"'Il(£ll-lU)1 (7.15)

These CQnel.'pts will be discussed later. For now. we will mention that this equation uses
two paramctcrs related to the difrercnel."S between the encrgy interactions £1.1' £\2' and
£o!..l' The ratios of the local mole fractions in these models will be expre.~sed with these dif·
ferences. For example, for It hinary system (see Section 7.6.3), we have:

where r2.1 '" exp - ( ~-'))


-(T I.l

It has been emphasized [Flcmr. 1976: McDermoll and Ashton, 19771 that such a defini-
tion does not rcspcctthe material balance imposed on the local mole fractions:
"ed
231

Taking inlo a«:ounl the fact that lhe sum of the local mole fractions is equallo I:
.(1.1+.1:1.1"'\ and xlJ.f.x u =1
we derive the following equation:

and onc condition relating to parameters Tl.2 and Tl.l:


1
--1
C'~:d'__ = ~
__ I .11

'"
that is not fulfilled by the preceding definition equation for these parameters. On the Olher
hand, the quasi-ehemkal model does comply wilh the condition [PanayiOlOu lind Vera.
19801·
We need to also menlion lhal lhe concepts we have presented do not include free vol·
urnI'. which in the case of a lattice model. is depicted by the difference between Ihe volume
of each lauice segment and the true volume of the molecules. We shall return [0 this point
in Chapter II. which is dedicated to polymer solutions.

7.5 REGULAR SOLUTIONS

The theory of regular solutions was introduced by Hildebrand [1924. 1970]. and lhen
Scalehllrd [1931].11 would be morc nalural and hislorieally accurate 10 introduce lhis Iheory
as being an outgrowth of the van der Waals equalion of Slale.of the mixing rules relaling 10
it (see Chapter 8). and of the work of van Laar 11910. 1913]. However. it may also be d,;,ve]·
oped from the conct:pl of local eOmposilion [Moelwyn-Hug.hes.. 1961. p. 1741 by calling upon
Ihe following h)lXllheses: the local compositions will be laken as lhe volumetric fractions:
..1"1.1 = .pl' Xu = ¢II' Xu = <Pl' Xu = <J)!.

and Ihe expression 7.15 for the exct:ss internal energy becomes:

Inspired by the expression for the dispersion energy and therefore limiting the applica.
lion of lhis model 10 mixlures of apolar oompounds (scc Chaplcr 3.1nlroduction) we have:
,
-21(ll,+,lJ)
VI z V
_(ll£U ZA.l)'
£1.2- - . ' - . -
z VI V

to obtain:
232

but the lerms between the square braekets may be expressed as a funetion of the residual
energy of the liquid (changed sign);

and the ratio of these residual energies and Ihe volume iIIuSlrales what we have termed
"the cohesive energy density of the liquid".
Notc that the law of composition defined in this way is especially simple. and may be
summari7.ed in the following expression;

"E = ,,/If = AI,ll>lPrlP 1

The solubility parameter of a compound will be defined by the equation;

.=('II·-'I?)~
, v;.r (7.16)

and we shalltherdore express the excess internal energy in the form:


"f: = vlP r tP 1(.5 r -.5z}" (7.17)
To get the excess Gibbs energy. we state thai the excess volume is zero. Excess internal
energy and excess enthalpy (heat of mixing) are therdore identical. Finally. we neglect
excess entropy such that we gel:
(7.18)

Note thai this modet can prediCI only posilive deviations from ideality.
This expression may be extended to a mixture of II components in the form:

(7.19)

The corresponding expressions for activily ooefficienlS for a binary mixture are:
• •
In Yr = Vt
liT (.5 r - 11. \1
"lJ
2
¢Jot In y! '" ;~ (.51 - .5lY 4>r (7.20)

and for tl components:


(7.21)

where 0", is the average solubility parameter of the mixture. calculated by weighting the
solubility paramclers of the components with their volumetric fractions:

(722)
We recognize the striking feature of this model: it requires only easily accessible quantities
such as the molar volumes of pure substances in the liquid state. v/.and the solubility param-
ClefS. These are defined by Equation 7.16 and may be calculated from the heal ofvaporization:
233

,
._(tJI'!-RT)'
, "i'- (7.23)

Their values are available in the literature and in the data banks. For enmple. below we
give the values from Chao and Seader [19611. who applied the theory of regular solutions
to the calculation of liquid-vapor equilibria.

T.1He 7.7
Molar volumes and solubility p>lra"""crs [Chao and Seader, 1961 J

Compound "

(cm l .moI-') •
(J·em,lf"' Compound

<<:nr'."mol")
,
(l.cm' J )'U

.........
Elhall<'

,,-Butane
."
101.4
12.38
13.09
13.77
""'1"~
BUlen<: I
Pentenc I
"
,OJ
110.•
tJ.l S
13.113
14.42

..
'''''
n·Pentane Cydohuane
116.1
'"'' 16.77
"·HexaM:
,,·Heptane
131.6
147.5
14.87
"2
12.44
Benzene
Toluene ",
89.4 18.74
18.25
Ethylene
" ,.-Xylene
'" 17.94

We nOle thai these authors look these parameters to be independent of temperature.


and they included light hydrocarbons in the range of application ror the proposed method.
The examination of the vallics of the liQlubility parameters it sufficient for predicting
the importance of the deviations from ideality. SO ....e can state that the values are not very
different from one n-alkane (0 the next. It is the same for paraffin to olefin. On the other
hand. (he liQlubility parameters of the aromatics are clearly higher. On the basis of this
model. we oondude that aromatic and paraffin hydrocarbon mixtures are not ideal.
Besides. we kno.... this from experimental values of the activity coefficients at infinite dilu-
tion (Table 7.1).

o EXAMPLE 7.2
Calculation of the solubility of elh.lne in benzene and
n.Heptane using the regular solutions model
The solubility of gases in the liquid phase depends closely on the deviations from ide·
ality of the liquid solution. We will look at the case of ethane (component I) at 25°C
and at atmospheric pressure dissolved in either boen~ene (component 2) or n-heptane
(component).
The calculation of the equilibrium coefficients ....ill rely on the application of the gen-
eral Equation 6.4:

(6.4)
.

,- ;;;;1 J
in ,til·' L

1 ,-1', 7 .• I ,-l~

'7,.' , '
.~

.1.
l. .'
L
L'

h It
236 i. Devi..lioos Iium """lily I" rhe liquid Phase

This application demonstrates the importance of the deviations from ideality ill lhe sol-
velll power of a compound. Solubility is high when the deviations are low (and possibly
"negative"). "I11is innucnce is apparenl in liquid-liquid solubility. solid.liquid solubility. as
well as ill gas-liquid solubility.
For lht! lhwry of rqullr solutions, ,,'t need 10 retlin the following ~nlial i'enn:
• Ringe of lIpp1ic1lion: mixtures of apolar mmpound!l (especially hydrOCll.rnoft$)
• A gcnerlllly salisflK10ry precision in tenns orthe cakul.tion of actirily rot."trlcienb
• MPndlcth'e" naillft',
Undoubtedly. due to this predictive nature but also because the entropy term was ncg-
lected. we cannot expect Ii perfcct estimation of liquid-vapor equilibria. and as for the
"key" pairs of a process. it is appropriate 10 go back to the experimental data. The example
illuSlrdted in Figure 7.11 (Jose fl al.• 19921 roc the benzene /l-telradccane system clearl)'

GI gE T_283.15

• gE T.293.15
• gE T.303.15
• gE T-306.15
• gE T_313.15

• gE T.323.15
, o gE T.333.15
~
0>
• gE T.~.15

•• "'" • gE gE T.35:i15
0 T.363.15

¢ gE T.373.15

F"'P"' 7.11 ExCC$ll (iibbs energy of 1M, benzene (I ) ,,·Iclradecane (2)


"l"'tem [..looe rrttl.. Ill92I.
237

shows Ihal the theory of regular solutions cannot claim \0 represent the variation of excess
Gibbs energy of such mixluTe!l as a function of composition and temperature.
Numerous modificatiOfls have been proposed to improve its aa:uracy. The most simple
consists of"coupling" the Aory theory (Section 1.3) and the Scalchard-Hildebrand theol)'
within the excess Gibbs energy expression by slBting:

(7.24)

As shown in the example from Figure 7.12.ll1e calculation of the activity cocffl'c1ents
approaches experimental data. We must. however. point out thaI application of Ihe Aory
theory 10 mi;dures containing arOmatic hydrocarbons is difficult to defend.
One modificillion. perhaps more empirical. consists of stating the expression for excess
Gibbs energy as:
• •
gt": ~v L L lP,41/l(o;-6/i+ 2k..A8,J (7.25)
1_1/_1

where the binary parameter ki,j is determined from eKperimental data. Note that the law of
variation with composition remains identical to the one predicted by Equation 7.19. with

2 ,,
,
,,
I! ,,
,,
,
, ,
f L' , ,
~ ,,
, ,,
,,

,, --- ,.,
Mole fractlon 01 rHlellllne
"
F1p~ 7.12 Calculation of the activity coefficients for the II-heanc (t)
bcnzcllC (2) .)'Stem II SS~ Regular M>lutions ( I; Aory
entropy tenn .. regular IOtulions: ( ).
238

only Ihe amplitude of the deviations from ideality adjusted [0 the experimental datil using
the kiJ parameter.
As .....e stated al lhe beginning of this section. tile regular solution method may be de.-el-
oped from the van der Waals equation of Slale. It also results from the van LaaT 11920.
1913] equations that describe the variation of activity coefficients with composition using:

A
llll':!'" 2.1 (7.26)
A"X,),
( A1
I. -
i

.2.f)

Parameter,; A l.l and Az'1 are determined from experimental data. However. if we nate:

Au:" ;~(QI-.5J2 and

we come back to the expression 7.19. which is "predictive" in the sense Ihat the parameters
IITC calculated from the properties of the pure substances.

7.6 EMPIRICAL MODELS BASED ON


THE CONCEPT OF LOCAL COMPOSITION

Whether formuJmcd from Ihe van der Waals equation of state or from the concept of local
composition. the regular solution theory distinguishes itself by its predictive eapaeity. Only
the properties that relale to the pure components are needed for ilS application. This is not
true for the methods that ....e will discuss now. They are characterized b)' the expressions of
excess Gibbs energy containing binary parameters whose values must be determined from
experimental data, coming essentially from binary liquid-vapor equilibria. The process
therefore appears similar to the one we used in Section 7.2 and would limit itself to a sin-
gle correlation of data if these methods did not lead to the calculation of high order.ter-
nary, or II component system equilibria once the parameters are identified. Such is the
character of the Wilson. NRTL. and UNIQUAC methods that play an essential role in the
practical calculations of liquid-vapor equilibria.

7.6.1 The Wilson Equation

The model proposed by Wilson is based both on the concept of local composition aod the
Flory theory. It is based on the assumption that Equation 7.9. to which the development of
this last theory leads. remains valid in the presence of molecular interactions with the
condition that the volumetric fraction <.Pi is replaced by the local volumetric fraction of
component i surrounding a molecule i. ~,:
2J9

ThC$C 1(1('31 volumetric fractions arc calculated from the molar volumes of the compo-
nenlS 11/. and the intermolecular interaetion energy. -\;:

We stale:

such that the excess Gibbs energy expression becomes:


• •
gt: .. -RT L XI In ( j.oI
i.1
L AI./X,) (7.27)

and the activit)' coefficients arc expressed by the equation:

In}';= I -In (± /_1


Ai,JX ) _
1
± ~x*
"I '\;' •
Au
L, "k.jXJ
(7.28)

i_I

ParamCle~ AI,j or J\iarc determined using experimental data (note thai the AIJ param-
eters must alw3)1' be positive). The Wilson equation has been applied to a great number of
polar or non polar sYSIl:ms. II allows for their correlation in a generally veT)' satisfactory
way. The prediction of liquid-vapor equilibria of high order systems is generally considered
weak. We CllIl sbow lIUlI.s1mply due 10 IU dI.Ilhl'm.ti~1 form. the Wilson equation mll)'
ne~~r be usecllO IUlUtnlle liquid. liquid demh:lng.

7.6.2 The NRTL Equation

The NRTL (NOll Random Two Liquids) equation proposed by Renon and Prausnitz
f1968] is based on the expression for the internal energy of mixing as a function of local
compositions discussed above:
I
u F. .. 1/.11 " - 2: 'll ZIX Ix Z.1{~.1 - £1.1) + z:x1 x 1.2( £1.2 - Cz.J1 (7 .15)

Given that Ihe degrees of coordination Zl and z: arc equal. and stating:
I
C,u"-i :'x:{E,;.j-£a)
it can be generalized 10 any mixlUrc:
• •
It': '" LXI LXj.,-Cj;
i.l '.1
240 7. Oevi<>tioos /ivm IdNliry In rhe Liquid PIw..,

As was done by Wilson. the local compositions were calculated llsing lile C~I parame-
ters. A third paramclCr called -non-randomness parameter", which is ill fact empirical. ill
introduced to yield:
xc~p(_a._Cj,l)
I IJ RT

wherea.. I-' "a".


I.

[\ is inserlcd into the expression for excess inlcmal energy. As in the theory of regular
solutions. we neglect the excess cnlropy and excess volume tcnns and thereby obtain the
\'aille of excess Gibbs energy:

• •
gr.~LXiL (7.29)
j. I j • I

The activity codficiems 3TC expressed by the equation:



L T;;G;JXj •
CUII
In l'i '='
Jo I
• ,-L, (730)

L Gt•.xj
i-I .,

L GlJX~

where: (731)

For every binary system. the NRTL equation therefore has three parameters that must
be adjusted to experimental data ClJ. C;.1 and a l .! '" ilz.1" In addition. it ha.s been suggested
to account for the variations of these parameters .....ith temperature by stating for instance:

(7.32)

We then have sill parameters. Deriving the gEl RTratio .....ith respect to temperalure and
applying the Gibbs-Helmholtl: equation, .....e obtain the ellpression for ellcess entbalpy
(heat of mixing), and the simultaneous correlation of liquid-vapor equilibria and the heats
of mixing is possible (Fig. 7.13).
In fact. the number and the character of the parameters that .....e may determine are mainly
dependent on the number and the character of lhedata we use, and the amplitude of the devi-
ations from ideality,assl10'0\-ll inTable 7.9 [Renoo tI al..1971,p.30]. We may account fOfparam-
eter variations with temperature only if the liquid-vapor equilibrium data elltend over a "'ide
temperature range. or if we can associate them with heal of mi:t:ing data. E\"Cn if we limit our-
selves to three parameters. the application to moderately non-ideal or weakly polar systems
will show that these paramctel"!i arc correlated. Ii is therefore suggested to rill parameter a.
since the "'standard'" values arc equal to 0.2 for weakly poIarsyslcrns.and 0..1 for poIarsystcms.
Ii has also been suggested that this same parameter be rilled at -I [Marina andTassios. 1973].

p'
241

'rei
'00

0' ",. r, ,

'00

o

-'00

tlpft 7.13 UK ofthc NRTL mood to the calculation of (a) liquid


vaporcquJlibrium at atlTlO6pheric pressure. and (b) heal of mixina
for the acetone (I) waler (2) s)'StCm!I (Renon n I>L. IWI].

The NRTL equalion is also applicable to the calculation of mutual solubilities in the
liquid phase. As shown in Table: 7.10. it allows for a generally very good representation of
liquid-vapor equilibria (bubble pressures and C()mposition of the vapor phase), healS of
mixing, mutual solubilities and activity coefficients at infinite dilution for. large number
of polar or non-polar binary systems. Table 7.11 summarizes a series of trials relalive to the
-:DlJle7

[ I Dmm~-'iD' leIS
-le::~.1

rh h "'

L [ I f ,

1 L. 1 ~'

L ~ . a.
1 L
I.

1 1

J
L I, 1.1
" OJ

-
.~

IQ...

, • • I:.ilLL.lfI f hr II
244 ,. De\>;'H/om from Idrnliry in rhe Liquid I'fusl!

determination of the six paramelcl1i of lhe acetone. hexane s)'llicm. We use the liquid_
vapor isothermal equilibrium data between -20 and 55°C. as well as activity coefficients at
infinite dilution for hexane in acetone al atmospheric pressure. the mutua] solubilities in
Ihe liquid phase between -90 and -4O"C. and finally the heats of mixing..
From one trial to the next. we have used a portion of this database for the parameter
calculation. and we can then examine to what extenl the data not used in the adjustment
are predicted. In particular, we obs!.:r\'c thai from the data for heal of milling and tbe
isothermal liquid·vapor equilibrium data at 20"C only. the full data set is predicted satis-
factorily (Trial 2). On the olher hand (Trial 7). using the mutual solubilities only is nOI
appropriat~ to predict either liquid-vapor equilibria. or the heats of milling,

II is then possible to calculate these same properties for higher order mixtures, with /I
componenlS. However. we musl emphasize the fact that the simultaneous correlalion of
the liqUid-vapor and the liqUid-liqUid equilibria is more delicate. The prediction of m~­
bllity gaps for complex s}'!;tems mOISt often requires that ternary data be available. A
detailed study of the possibilities of this method and the caletllation programs that relate
to it have been published [Renon 1':' af.• 19711.
llte local environment could have been defined in terms of volume fractions. as pro-
posed by Bruin and Prausnitz (19711. This approach has the advantage of-containing" as a
special case. the regular solution model if the a parameter is null. Under these conditions.
for a complex mixture the parameters that relate to Ihe binary hydrocarbons may be cal-
culated a priori.

7.&.3 The UNIQUAC Model

The UNIQUAe. MUniversal Quasi Chemicaf'. model !Abrams and Prausnitz. 1975:
Maurer and PrnusnitL 19781 is i!$elf also based on the concept of local composition.
However. it expresses the energy balance of the miXing operation by taking into aerount
the external surfaces of the moleeules. The molecule of component i is broken down into rJ
segmenlS. and ilS external surface is described by a parameter q/. Using z to denote the
coordination number. the molecule of component i is in contact with zq,segments belong-
ing to neighboring molecules. If we take component i as being pure. in order to remove a
moleetlle from its environment. we must furnish energy equal 10 z q/ cu' In the mixture. it
is surrounded by zq/ segmentS in proportion 10 8iJ.lts condensation will be accompanied
by an energy transfer equal to ~, zQ/8iJcjJ •
The equation (analogous 10 expression 7.15) expressing the internal energy of mixing is
therdore:

We state:

p'
7_ Devi~lions irom """'lily in rhe liquid f'toM,e 245

and with 9j as the global "surface" fractions:

we determine the local environment with the equation:

..
2",9~ ft./

where:

resulting in the cxprcssion:

In opposition to the approach used for the NRTL model. and this is essential. we apply
the Gibbs-Helmholtz equation in order to calculate the exccss Helmholtt: energy:

" c
aRT
a~1
=-
R
therefore - =
RT
" f' ,,' (')
l..R
-d-.Q
T
T , '.
selling the integration limit To approaching infinity. At high temperalllre. it is assumed that
the interaction term is zero such that the integration constant is obtained from thc combi-
natorial entropy expression of St8Vennann-Guggenheim (Eq. 7.13):

(7.13)

As the integration result relates to Helmholtz energy. it is assumed equivalent to Gibbs


energy sincc the excess volume is low, and it is designated using the tenn residual excess
Gibbs energy:

(733)

so finally we have:
(7.34)
7. De\";ariorn iron, IdroUty in rhe Liquid " " - 247

If "-I' stick to the calculation of liquic!·"aJlOf equilibria lind the Wilson eq....tion. the
NRTL IUId the UNIQUAC models yiek! romparable results, and are gene...lly ItCCUrate.
The calculation of hcats of mixing by application of the Gibbs-Helmholtz equation is
generally possible only if we take into account parameter variation with temperature.
which doubles their number.
As for liquid-liquid equilibria. we retain that b.:cause of ilS mathematical structure, the
Wilson equation does not represent demixing. On the other hand. the NRTL and UN 1-
QUAe equations may be llpplied to the correllltion and the prediction of Ihese phenom-
ena.
Pll,.mder determination, whose principle ..lLS explainecl in Section 7.1, mll\t adhere tl)
the mit'S of rommon sense; the amount and the nlltore of the llmlable da.a must be
respeaecl. For example. we can account for the variation of parameters with temperature
only if we usc either equilibrium data within a wide temperature range. or equilibrium
data plus heat of mixing data.
Similarly, if we wish to apply the NRTL equatiOn or the UNIQUAC equ.atlon to the cal-
culation of liquicl-li.quid equilibria. "'I' must not be 5lItiJified ..ith pa",mden ddermined
from IIquld'VIlpor equilibrium dalli. The latter. within the full miscibility region. may he
....1'11 correlated or predicted. and the solubility boundaries represented in a qualitative
fashion only because of the extreme sensitivity of this type of equilibrium to aClivity coef·
ficient values. The experimental database must therefore include binary liquid.liquid equi-
librium data and, preferably. ternary data. for there 10 be any hope of an accurate predic-
tion of the .'" componenf· mixture.
Endo....ed with three parameters. the NRTL model is. in principle. able to be applied to
a very large spectrum of devialions from ideality. This is also a ....eakness because their
simultaneous determination requires more data.
F1nlllly...'e shllll be autious for the ri~k of parameter inteM:OTftlation. For a gh<en
binary data base. it may happen that an entire set of parameter pain represents the exper-
imental base equally well. [n a way. too many parameters are dealt with. Application of the
models jusl diseussed to mixtures of non·polar compounds. and espec;ially hydrocarbons. is
an example of such a phenomenon, To eliminate this lack of a unique solution.....e may be
led to insert a relationship between the parameters. their equality, for example. in the case
of the UNIQUAC [Soave. 19921 model. or to ·'enrich·' the database with new measure-
ments that are more accurate, or of a different character. For example. an inter-<:orrelation
of parameters relating to some binary systems can be eliminated by using ternary data
related to the same systems.
In any evenl, application of these models to a comph,x mixture involves a considerable
amount of com:,larion. Let us not forget thaI a S~lem made up of ten components.. which
is nothing exceptional in practice, contains 45 binary s~tem:l. "o..e"er. tbere Iln' dlltll.
bllSe!llhllt, for II large number OrliystemS,lipeciry Ihe VIlJUe5 for the p.,.meten orthe mod·
els we han Just introduced in IIddilion to the experimental dlltll. The best known and the
most abundant in data, is the one started by the Uni\'crsity of Dortmund IOmehling J. and
Onken u.. 1978). An example of its contents is given in Table 7.12.
Vet it happens that no eltpcrimental data n:lating to the studied system is available. If
this system is one of the ~key pairs·· of a separation, ....e must then ~go back to the lab~.
Otherwise, ....e can apply a ·'group COntribution·· method.
250 7. Devi"riorn from Ideality in roo Uqw'd Phd..,

Proposed Wilh the intent of 11 more widespread application. the ASQG and UNIFAC
methods both adhere to the firsl and third propositions and h)'potheses alluded 10 by
G.M. Wilson [19621;
• The partial molar excess Gibbs energy:

(5.75)

is the sum or two contributions. the first. referred 10 as combinatorial. corresponds 10


lhe differences of size and fonn of lhe components of the mixture. and Ihe second.
called residual. corresponds to lhe interactions between groups. We therefore have:
(7.39)
• lhe residualtcrm is estimated by substituting Ihe notion of "group solution for the
M

notion of chemical compound mixture. Rwexample. in a mjll:ture containing one mole of


hexane and one mole of acetone. hc:o:ane supplies 2 moles orCH J groups and 4 moles of
CH 2 groups. and acetone 2 moles or eH] groups ami one mole of the C=O group. The
molar composition of the ~group solution"js therefore 419 for the CH J groups.419 for the
Q-i! groups and I~ for the C 0 group. Of course.. the componentS themselves \\ill be
COllsidered "solutions of special groups" since the composition of he~ane is ']Jf, for CHJ
and 416 for the CH! groups. and acetone is 213 for CH J • and 113 for the c=O groups..
These group solmions are not ideal and each group k is charactcri7.ed by its mole frac-
tion X~ and its activity coefficicnt r•. Thc residual activily coefficients themselves, y;.
are related to them by the expression:

In r.'~~ = L "l.i (In r.-In r•.;) (7.40)



where "•.1 denotes the number of groups k in component i. r.. /the activity coefficient
of group k in the mixture of groups that make lip pure compound i. and r~ the activo
ity coefficient for the same group in the actual mixture.
The difference between the ASOG and UNIFAC methods results from the models that
have been selected to express the combinatorial and residual terms. as well as the defini·
tion of groups. They were the subject of a comparison by Gupte and Daubert [1986J that
does not anribute a decisive superiority to either of them. We shall more fully develop the
more familiar UNIFACmodcl.

7.7.1 The ASOC Method

Introduced by Wilson [1962J and Dcrr and Deal 11969]. this method has been de"eloped
by Kojima and Toehigi [1979[.lInd then by Tochigi t'l 0/. [1981).
We apply the general expression for activity coefficients 7.39 thal has just been intro-
duced. and Equation 7.40 for the calculation of the "residual" term.
The oombinatoriallerm is expressed starling with the Flory theory where \'/ designates
the number of atoms comained within component i. with the exception of the hydrogen
atoms. We have:
7. Devidrions tiom ldedliry In rhe Liquid Phd... 251

(HI)

For the residual lerm, the activity coefficients of groups r~ lire calculated using the
Wil!\On equation:

(1.42)

where Xl is the fraction of each group I in the mixture:


~ x/vl.j
I
Xl'" (7.43)
LXILvtJ
i •
lind VI/ is the number of groups I in component i,
The inleradion paramcters between groups 1Ik.lllre temperllture dependenlllccording to:

(7.44)

where m.,1 and ".,1 were obtained by liquid-vapor equilibrium data regression.

7.7.2 The UNIFAC Method

The UNIFAC method was proposed by Fredenslund ell/I. [19751.11 nows directly from the
propositions defined by Wilson (Eqs. 7.39 and 7.40) and the UNIQUAC method. The com·
binatoriallerm is talculated from the Stavermann-Guggenheim exprCSliion:

(7.13)

from which we obtain the expression for lhe activily coefficients;


0· z 6. 4>1~_
In Yi...-,ori.aI '" In ...! + - qlln ...!. + '/- - U'jlJ
xj 2 4>1 Xi
,
,, = 2' (ri-q/)-(fi-I) (7.36)
where z '" 10

In order to calculate the volume and surface fractions of the components we need to
know the corresponding molecular parameters f; lind ql' these being calculated from the
volume and surface parameters from eaeh group R. and Qk using simple additivity rules:

f;'" L: 1'k,IR•• qj= L: I'k"Qk (7.45)


• •
. , - 1 -
--~ ..... _-

conl'poneD~m .

,
1
- -
I
··1 .-

I- I -

n ' ~ ,OMl'IibilliJ:t • I l

In

l'- Ib-

-. - - - !Ii

U1rt.f"C· LIlt
256

, 2
XI I '" 1.1 = = 0.5. Xu '" 0.25. X 3.1 = 0.25
. vu+v~.I+\').1 2+1+1

and we derive Itlc sorface parameters:


Q1XI.l 0.848·0.5
91.1 = = = 0.496 5
QIXU + Q2'''l.l + Qy\'J.l 0.848·0.5 + 0540·0.25 -+- 1.180-0.25

~1=O.1S81. 8.tl=0.3454
Equation 7.46 remains 10 be applied 10 oblain the values (or 'il' For eX~lmple, for 1"1,1:
I-In (8I l1'L1 -+- l3:!¥'l.l -+- 8)".).1)
8 1 ¥,u

which is:
1 -In (0.4965·] + 0.ISSI-1 + 0.345 4-0.927)
0.4965·1
0.496 S· I + 0.1581· 1 + 0.345 4·0.927
In 1"1.1 = O.1l4S
0.1581·\
0.4965·\ + 0.1581· J + 0.345 4·0.927
0.3454·0.2595
0.496 5·0.2595 + 0.1581-0.2595 -+- 0.345 4·]

and therefor.::

In '-1.1 = O.Il48[1 + 0.025 5 - 0.5093 - 0.1622 - 0.17301" 0.1527

In the same way. we find thai r1.1 = 0.0972 and In ["J.l = 0.4368.
A similarcalculalion is thcn applied 10 the mixture il!>Clf. We determine the mole frae-
,iolls for each group in the mi~!ure (Eq. 1.48). For the firs! group:

2 -0.056 -+- 2 ·0.944


'" '" 0.2914
2·0.056 -+- 2·0.944 -+- I ·0.056 -+- 5 ·0.944 -+- I ·0.056 -+- 0·0.944

nnd similarly rOT X 2 '" 0.69906 and X J '" 0.0082.


The surracc fractions Ihal correspond 10 these compositions (Eq. 7.41):

9 1 ",0.3901 ~",O.5941 ~",O.OI522


~ .. IJ

~1

] 1-
-1. 7

-In' .J
[ .'

11

In 1'i.- '-7

7'73 [GroUD UI ,~
&L d'_

'p
260

T.b&.'.U
Cu....elalion 0( liqllid·~aporequilibria oflhe chloroform (I) acclone (2)
system at 313.15 K using llle associaled ideal ilOlutions model

,...
<,
0.0000
0.0303
,~

56.5700
SS.630tl
,~

56.5100
55.4970
0.0000
0.0140
~ ,,~

0.0000
0,0121
....., •
1,

0.4598
"''''0
0.9995
<
n.mo
0,0139
'.
1.0000
0.96\12
0.0834 53.ll800 SHill I 0.0407 0,0366 0.4888 O.99S8 0.0408 0.9127
0.1431 51.9300 51.4435 0.0750 Om02 0.5247 0.9867 OmS] O.84SS
0.2082 49.8200 49.1425 0.1189 0.1157 0.568' 0.9701 0,1183 0.7682
O.287~ 47.2700 46.S090 0.1844 0.1865 0.6268 0.9391 a,HI)4 0.6688
4Hl800 0.2686
0.3616
0,4270
0.49711
43.4200
42.0400
44.4002
42.9336
41.8867
O.2S\l5
0.3385
0.4365
0.3-"0
0.4562
0.6&58
0.7401
O.79ll2
"""
0.8557
a.1Il18
0.2480
0.3160
0.3974
0.574 I
0.4903
0.4026
0.5628 41.2900 41.4129 005340 0.5536 0.8483 0.7486 0.4n4 0.3273
0.6018 41.0\l00 41.4746 0.5937 0.6111 0.8757 0.716\ 0,5210 O.28S2
0.6381 41.0700 41.6333 0.6484 0.6626 0.8990 0.6861 D.S737 0.24113
O.6115S 41.3000 42.{WSS 0.7169 0.m9 0.m9 0.6477 0.6347 0.2037
0.730S 41.9300 .2.6207 0.n67 0.7808 0.9<173 0.6126 0.6920 O.\Ml
0.11039
0.8602
43.2500
44.5400
43.85S7
44.9190
0'"''
0.9120 0'"''
O.908l
0.9738
0.9874
0.5S97
0.5227
0.7828
0.8494
0.1091\
0.0731
1.0000 48.0900 48JI900 1.0000 ureo 1.0000 0.4444 '.IXXlO 0.0000

ro.,---------,

'"

"'+--~~-~-.,--j
0.0 0.2 0.4 0.6 0.6 ,
MolllIraetiDn of chIoo olui III

1"1pri17.U Applicatioo of l~ aU/Xiate<! ideal solutions model to the


chloroform (l) acetOollC (2) S)'$tem.
Cur·..e'<: calculated values: points: experimental values [GOflII ~I aI.• 198..'i].
1. Devi.lrionsli'o-n Idrnliry in rhe Liquid """'" 261

Wilh alcohol hydrocarbon mixturn one of the components in the pure state is "poly·
merized" by auto-association. and Ihe measurement of ils vapor pressure is in fact for a
polymer mixture. According to tradilional laws or equilibrium displacement. the addition
of an inert solvent. the hydrocarbon. will cause the polymeriz.ation reaction to regreM.
release the more VOlatile forms that are le!ill combined. and Ihu~ be responsible for positive
deviations from ideality. corresponding to what is observed.

GeMnl Equations (or A5s0ciated Solutions


The model for associated ideal solutions is very much simplified. We know that the hydro-
carbon mixtures arc not ideal. and we do not know whether it is caused by an association
process. We are therefore led to suppose Ihat in an associated solution. the actual chemical
entities themselves make up 11 non-ideal solution. This fact results in generally complex
models.
There are. however. some general equations thai we shall illustrate using the case of
solutions with an auto-associalive compound (alcohol. for example) in an inert solvent.
They lend themselves to more complex cases.
Let us denote the auto·associative compound A. the solvent B, and state the stoichiom·
etry for auto-association:
;=2.<>0 (7.50)

The apparent number of moles of component A. N(A) and the (real) number of moles
of component B. N(B) are known on the basis of the mass of the components and the
molar mass of the monomer for A I and of solvent B. On the other hand. we ignore the
number of moles for each of the species Ai' N'(A 1). The material balance, however.
imposes Ihe relationship:

N(A) .. L, iN'(A I ) (7.5\)

Furthennore, the ~ elftenlS of these reactions are such that the Gibbs energy of the sys-
tem G al the given temperature and pressure. is minimal. For each of them we have:


dN'(A1)=-L id(1
,
The elemenlary variation of Gibbs energy corresponding to the progression varialion
d;1 is therefore (as a function of the number of moles and actual chemical potentials):
• •
(dGhl'=L, ~'(AI)dN'(AI)" L lJI'(AI)-i~'(AI)ld(l
,
and the minimum condition imposes:

(7.52)
263

7.9 IONIC SOLUTIONS

Deviations from ideality for ionic solutions result in 11 large part from long distance inter.
actions between anions and eations. solvation of ions. and lhe fannatio" of ion pairs. To
this is of course added the interactions due to aUrael,on forces exerted between the sol-
vent mol«ules at average distance. and repulsion at shorl distance. as we have already
encountered.
Thf,.'SC deviations from ideality lIrc evidenced in electrochemistry. btU also wilen deter-
mining phase equilibria: Ihe precipitation of salts from a saturated solution. splitting of twO
liquid phases. and liquid-vapor equilibria. For example. an 8:r.eQtropc may be substantially
displaced or even eliminated by lhe addition of salls.
Ion activity cannot be estimated individually due 10 the clectroneuuality condition Ihal
prevenlS a solution from conlaining a single species and. because of Iheir absence in the
vapor phase that does not allow us to obtain Ihe liquid-vapor equilibrium coefficienlS for
each one of them.
We shall neither discuss nor summarite the thermodynamics of ionic solutions in this
study. The reader is invited to consult the works of uwis ~, uf. [1961. pages 298 to 3121.
Robinson and SlOkes [1965). the Cruz Journal [l1l77J. and the articles by Pilzer [1973.
1979J.Chen [19791.and Renon {1979).
Instead. we shall summari1:e the example proposed by Sander e, ul. [I\I86J and Macedo
(!f al. [1990) for Ihe calculation of liquid-vapor equilibria of electrolyte solutions. It uses an

extension of the UNIOUAe modcl already introduced in this chapter.


Only the solvents are involved in the Iiquid,vapor equilibrium. Therefore. this model
limits itself to the calculation of activity coefficients of the solvenl(S). yet lakes inlo
account the changes caused by the prescnce of ions. The model statcs the liquid-vapor
equilibrium condition using the traditional formula:
(I' _ (L
1/ - 11

Prj",r '" Pi' fPi''P/X/ r,L

Since the model was developed from liquid-vapor equilibrium dala at low pressure. Ihis
condition is reduced to:
p"., ~ P"x
I I,'.
,

and in these equations rr represenlS the activily coefficient of the solvenl or solvents.
defined from the usual reference Slate (pure substance). Three contributions stand out in
the activity coefficient expression:

(7.54)

l'he firsl Icrm is from the Ocbyc and Hucke! [l923J theory. which is explained in the
prescnt case by Cardoso and O·Connclll987J. The second teon is the oombinalorialterm
from the UNIQUAe model. Which has not been modified. The third. or residual term.
retains the form defined by the UNIOUAC model. but the calculalion of the interaction
parameters accouOlS for the presence of ions.
264

The Debye and Huckellerm is exprC5scd by the equation:

2AMd.[ 1 ] (7.55)
lnr;,lJ.Il'" bld; , l+bv'f- + Vi"-21n(l+bVl>
1 b

where:
,,' b = 6359696 Td.
Ya
All being the molar mass of oomponcm i, djlhe density (expressed in kg/em). d, the sol·
vent density (or the solvent mixture). [the dielectric constant. J the ionic force. lind T the
temperature.
The expression for the rcsiduallerm remains unchanged:

(7.37)

where the expression for the interaction energy as Il function of temperature is:

Tp=exP(-~) (7.56)

In the presence of electrolytes. the IJj,i parameters will be II function of the oomflOliition.
If subscript i is a solvent, and the SUbscriplS j or k are ions. we have:

(7.57)
Q. -
'I
= II~ + 8·2 I.V:;.>.,
It.,
The parameters of Ihis modd (volumes and surface of the ions. the interaction temu
ai.l' OJu) were calculated for as much as experimental data existed for the solutions where
the solvent was: water. methanol. ethanol. II-propanol. acetone. and n-butanol. and the
alkaline cations. alkaline eanh salts. nickel. mercury, the halide anions. acetate, and nitrate.
All in all. Ihe results were excellent.
We might imagine II model based on group contributions. However. its development
would be hindered by the lack of experimental data in sufficient quantity. The same would
be true for its extension 10 liquid·liquid equilibria and the precipitation of salts al satura-
lion.
265

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venllsall SyslemS usinS an extended UNIQUAC equalioo. ClI~m. E,,1f. Sci,,41. 1171-1183.
Soa"e G (1m) Application of the UNIQUAC equalion 10 regular Klluliom. Fluid Pha... Eqllilibri",
77,133-137.
2.8

Skjol<l.Jorsenscn S. Kolbe a. Gmehling J. Ra~mugcn I' (1979) Vapor-liquid equilibria by UNlfAC


group rontribul;on. Revision and Ulen51Qn./nd. £ItS. Ch('m" Procus Do. Dt\'.• lll, 714-722.
Sla •..,rmann AJ (19S0) The emropy of polymer ..,lulions. R~ Tnn'. Chim./Ile Net/lu/umb.. fiJ. 16J.
TlCg$ O. Gmchling J. Rasmussen P. Fredensilloo (1987) Vapor·liquid ~'qll;libria by UNIFAC group
contribution. Revision snd extension 4. 'nd. eng. Chl'm. Ru., 26. 159.
T/Xhigi K, Lu BCY. ~hi K, Kojima K (1981) On the tCmpcnllure dependance of ASOO pammele...
forVLE calculations. AICh£ J.. 27.1022-\024.
Trejo LM. C<>!:las M. Pauerson D (1991) I",,,,muwnal 0..", Suin. A series, Selected Data on
Mixtures. p..'iO.
van Ul.ar JJ (1910) S.,eh, VOl1rl1ge IIbe. das 1lH:rmlXlynami.chc PIltcntial. Z. "/,,-sik. eh"",. n. 723
and 83. 599.
V(r~ JIl (1986) On local oofllpoe;ilK>m; _pI. Fluid Plulu EquiJibru.. 26. 313-316.
Weidlich U. Macedo E. Gmchling J. RlISmllsscll P (1m) Vapor-liquid equilibria by UNIFAC groop
contribution. Revision and eXlcnSK.m 3. 'lid. E"6' Ch"",.. ProalS DUo Dn'.• 22. 676-678.
Weidlich U.Gmc:hlingJ (1987)A modified UNIFAC mood. I. Prediction orVLE.lrc.and r. trod. £Illt-
Chtm. Res.. Ui.I372·1381.
Wil~ GM. Deal CH (1962) Al.1ivily coefficients and molecularSINI.1Ure./"ti. Eng. eire",. Fu"d"",..
1.26-23.
Wilson GM (196-1) Vapor liquid equilibrium. XI. A neW expr~-ssjon for lhe free energy of mixing.
i.Am. Chern. Soc. 86. 127·130.
Zudkevildl D (1978) ImpKl of lhermodynamic alld nuid propcrtlC!1 on design and toonOlt1lcs of
IICparation proceMcs, EItI:yc/opt:di.. of Clrm,kal Processi"tllUld Design. J. McKetta.

p'
270 8. loppIic~lkJn of f'l""'rjotu of St~re /(> Mi... rures

Robinson [19761 equation of stlite).lIpparenlly they are two in number.• and b. Since they
are most often calculated from the critical points and the acentric factor, we can also say
thaI these last quantities are the actual parameters. and thai it is appropriate to apply the
mj~ing laws \0 them. We shall see thallhis has been done.

Most oflen the mixing laws respect the structure of the equation of state, such thai we
implicitly form the hypothesis Ihat a mixtlin of liven romposiUoD beh.n~s like an utifi-
rial pure substance; we therefore han a "one Ouid mocWl". This is a hypothesis thaI noth-
ing substantiates., other than its simplicity and the results obtained.
The fact thai the application of equations of stale to mixtures and the calculation of
liquid-vapor equilibria are practically inseparable. leads us to carefully specify the calcula-
tion method for partial molar quantities. in particular chemical potentials and fugacity
coefficients. Certainly. the definitions and the equations developed in Chapter 5 apply. but
in practice we need to account for the structure of the equatmn of state and the mixing
laws that we choose. For the principal examples that will be mentioned here. we need to
make this point clear.
Finally. a fundamental question must be asked. For a homogeneous phase. the extensive
properties and their partial molar quantities can be. at least in principle. expressed and cal-
culated using two distinct paths. The first one we described and applied (Chapters 5 and 7)
uses reference states. mixing quantity. and eltcess quantity. The second uses equations of
state and mixing laws. Insofar as the models pertaining to each of these paths both addreliS
the problem lind have been selected. we end up with the same result. Consequently. an
implicit relationship exists between these two paths. Defining this relationship has led to
new mel hods lut, in design, combine the ~ ...l;ons of 51.te.nd excess qu.ntitia, .nd .5
such lhe qull1itit'll of eKft of these p.ths.

8.1 EXTENSIONS OFTHE CORRESPONDING STATES PRINCIPLE

These extensions have already been mentioned (Gapter 3.Section 3.2.3.2) and it is within
the framework of the Lee and Kesler 11975] method that they are most often utilized. Yet
they may be generalized for many other methods. as the eltamples that follow will show. In
particular, they are used in equations of state that apply the corresponding states principle
for the calculation of the parameters of pure substances. An example of this generaliZlltion
is provided by the work of y~ [1990] who, for the calculation of the speed of sound. com-
bined. on the one hand. the equations of state of Soave-Redlich-Kwong. of Peng-
Robinson. of Simonet-Behar-Rauzy. of Benedict. Webb and Rubin as used by Lee and
Kesler. with. on the other hand. the mixing laws that we shall discuss. A$ an eumple., the
equation of state from Soave-Redlich·Kwong that we introduced in Chapter 4 tlsing:

NT .(T)
p= - - - (4.42)
v-b v(v+b)

R2Tl
.(T)=O"T"(T,) (4.43)
<
272

II was modified by !'Iocker ef al. (19781 ror the purpose of belter calculating the Iiquid-
vapor equilibria. [t Iherefore has a binary parameter k jJ Ihal may be adjusted to experi-
mental data. Equation 3.36 is replaced with:

(8.4)

where: (8.5)

In works rel:lled 10 Ihe calculation or densily in Ihe liquid phase. Spena:r and Danner
119731. Hankmson and Thomson (19791. and finally Teja 119801. proposed the following
ruks.
Spencer and Danner rules:

LZlv~JT~.J
(8.6)
Lzjv<:j

(8.7)

Hankinson and Thomson rules:

(11.8)

(8.9)

RT,....
p"," '" (0.291 - 0.08 Ill", ) (8.10)
',~

wilh the linear Equation 3.38 being applied to the calculation of Ill",.
The TeJa nm;ing law has lWO adjustable pammeters ~.I' and "1./' which. in the absence of
binary experimental data. we shall lake 10 be equal to 1.11 is written:

(8.11)

(8.12)

(8.13)
27J

(8.14)

RT -/
PdJ -z
- <.II II
<.I. (8.1S)
r.• J

finally. Pedersen etal. 119841. in order to predict the viscosities of complClI: miJlIures..
applied lhe (ollowing rules:

(8.16)

(8.17)

Indispulably. these rules 3n: the product of much empiricism.


Figures 8.la and 8.th show the change of pseudocritical pressure as a function of pseudo
ocritical temperature for the methane ,,-octane and the ethane benune S)'$tems respec-
tively. Evidently.differences appear as a function oflile method thai has been applied. with
the exception of those from Hankinson and Thomson on the one hand, and Teja on the
other hand that lead to identical results if the binary parameters ~I' and lfiJ.rc both taken
to equal I. The differences are rdatively small in the case of the second system. However.
one should account for the composition. and Table 8.1 specifies the pseudocritical vailies of
the equimolar mixtures for each system.

TabkLI
Psclidocrilitl!1 points of tilt: equimolar mixtures methane n~.ne.
and ethane ben7.ene

~
Methane, II--oc:tane Ethane, benzene
Rule T~ p~ T~ p~
(K, (MPa) (K' (MPa)
K>, 379.70 3-" 433.75
,,,
'.89
Spe~r rr
Lee cr ../.
Plockerciol.
01.

Hank;n$OfI cl ..I.
504.74
425.02
362."
410.23
3.73
338
3.06
3.45
469SS
..D(
426.99
",-"
.,."
..,
'.Ol
l1:ja
Pe<kncn ~ ../.
41023
429.48
3.45
3.50
",-"
443.4
,."
'.Ol
274

",-----------,
,.--. ,,
,,
, ,,
,
,,
,,

•., ••

••

••

••



••
3.'
••
••

'i~ ..
~. "
3
.
..........., ",.
'~ '

,., ........... '


300
TemplInlture (K)

fl&u",8.I. Psoeudocritical coordinates of lTIl:lhanc. n-<JCtane mixlures.


Kay Method: : Spcntt. and Danner. :
~ and K«lcr: : Plock". '" 111.: ._._._:
Il:lJIkill5Ql\ and 1lIom>on: ._._._: Teja rl uJ.; _,._.._:
Pcrdenen '" ..I.: ...._.__ .

Of course. it is important not to confuse the pseudocritical coordirmles. which are the
parameters for a modd only, with the ··truc~ critical coordinates. The true critical point
(Chapler 6. Section 6.1.2) relates 10 conditions of temperalure and pressure that charac-
terize a real. experimentally observable physical phenomenon in which the two phases in
liquid-vapor equilibrium become indistinguishable. They may differ considerably from the
pseudocriticaJ coordinates. For example. in the elhane benzene mixture. the critical pres-
sure reaches 10.5 MPa while the pseudocritical pressure docs not go above 5.35 MPa. For
hydrocarbon mixtures with very different molecular weights. critical pressure may reach
several hundred bar.
277

Furthcnnore. by application of the Gibbs·Helmholtz equation we can write:

('~T~' l".:( ~'a~') L" ~ (~':f) L,:;,.-h;;" T~


therefore:

N ( Olnrp... ) ar,
-:=.---;;;;:;rT T 1 -o-h-h' (T )h-h
0---l(To 1

--I) (8.19)
, aT, T.f!'vi aN! RT '... ' T<.<fl RT,... T, T<JII
A series of analogous calculations yields:

N "",) ai',
-=-(2-1 )( -
i'o- I ) (8.20)
(
, ap, r:1'.N! aNi P,,,,,
Finally. applying II linear mixing rule [0 the acentric factor gives us:

And ultimately:

h-h' (T
1 -u- 1 ) -(Z-I) - - 1
In19;=lntp... + - - -
RT,,,,, T, T,.""
(P,,)
P"",

... (""aw.. ) '"


UNj
( Cll, - w".) (8.21)

If we apply the Lee and Kesler method thaI uses the simple fluid properties (w=O) and
the properties for a reference fluid with acentric factor r.J'I. for any residual term. lind
especially for the fugacily coefficient of the mixture. we slate:
(In rp)("_ (1n rp)IO)
'" .. 0 <', ,)(0).;. w... w(,l

and the preceding equation becomes:

1o '1';= In 11'. . + h-h"(T,,)


RT~",
T Te-
- - - - 1 -(Z-I) --'--1 (P,,)
P"""
t

(In rp)(tl_(ln rp)(O)


+ ",(t) (cq-w".) (8.22)

8.2 VI RIAL EQUATIONS OF STATE TRUNCATED


AFTER THE SECOND TERM

At this point. we shall return only very brieny to thl$C equations. An Cllamplc of their
application to the calculation of vapor phase properties wu discussed in Chapter S. Recall:
8
Z= I +- (4.13)
"
278 8. ~I;cdriot> 01 Eqwrions cI Sldte 10 Mixru~

for the equlllion derived from development in density, and:


8P
Z:::I+ (4.18)
RT
for the equalion cOlTesponding to the development ill pressure.
In either case. lhe iJeCOnd .iri.l roemcient 8 is ~I.ted 10 the c:ompmiltons by • qwtd-
I'1IIlk mixing rule. thal can be demonstrated by statistical mechanics:

(5.11)

which is.. for a binary mixture:

The re:;;idual properties 3rc calculated wilh the equations established in Clapler 4. For
the fugacity coefficients in a mixture. and for the development in prCSl;ure truncated afler
the sc<:ond lerm. we hu"c:

(2 ~8IJ)lI- 8)1'
RTln qI;:::
, (5.56)

As we have already emphasized. these cllpressions should be applied only 10 the vapor
phase at 10.... pressure. This application is common when calculating liquid-vapor equilibria
with the equilibrium ooefficiel'lt e~prcsscd as il'l Equatiol'l 6.4. al'ld it is I'lormal to acc::oul'lt
for Ihe correctiolls inlroouced when we make use of high precision e~pcrimelltal data.
cven if the pressure is dose 10 atmospheric pressure.
The main problem is knowing the secol'ld virial coefficients, especially their binary
terms 81,}' We rarely use e~pcrimental data for these terms [Dymond and Smith. 1980].
We have already discussed and applied the Tsonopolous correlation (Chapter J.
Section 3.2.2.1) 10 pure substances. II may be extended to the calculation of the binary
terols by dcfinil'lg the binal)' parameler:s To.•}. P<.L/' and 00,1' This has been done. We apply
the following eQulltions (among which we reoogni1:e some thaI have been previously
mentioned):

(8.23)

(8.24)

where: (8.5)

and: (8.25)

and finally: (8.26)


279

8.3 EQUATIONS OF STATE DERIVED FROM


THE VAN DER WAALS THEORY

The range of application for the virial equation of state is narrow.


II is certainly possible to calculate the liquid-vapor equilibria under pressure by
applying one of the o:tcnsions of the corresponding states principle mentioned above.
C$pecially lhe Lee and Kesler method [1975} as modified (or this purpose by Plockcr
t/Il/.II978}.
However. it is the equations of state derived from the van der Waals theory Illal have
provided the most satisfactory solution. 11 is the most commonly applied solution to this
problem. Here we sholl look 31the equations using the general exprc$Sion:
RT •
p" -,-~-b ~ (C,:ObC,C,)C(C'-~~bC,,~) (4.50)

in which the values for parameters '1 and '1 are characteristic of the equation in question.
as secn in Table 4.6.

8.3.1 The Classical Mixing Rules

In general. we l:ombine thcse equations of state wittlthe so-called "classical" milling rules:

(8.27)

(8.28)

.....here: (8.29)

In the preceding expressions the terms ai,i and bl are the parameters for the pure sub-
stances.The cakulation of the a(jbinary terms makes usc of parameter k(j.called the inter-
action parameter. determined from experimental data for phase equilibrium. We shall
come back to this term.
As before. the composition of the mixture is designated by I/. When lhe system is sepa·
rated into t.....o phases. the Equations 4.50. and 8.27 to 8.29 are applied to each phase. It is
understood that the corresponding composition. x/ for the liquid phase. andy/ for the vapor
phase (see Section 8.5) arc at .....ork. At a given temperature and prC5Sure. the equations of
slate may be solved. and the proper root assigned to the phase in question. The thermody·
namie properties are then cakulated for one and the other phase by applying the equa·
tions from Table 4.6.
It is important to point out tile relationships that exist between the classical mixing rules
and the regular solutions theory. They make the following cakulation possible.
281

are analogous 10 energies per unit of volume. such thai the pr«cding equation may
be compared to the equation pertaining 10 regular solutions (Scalchard-HiJdebrand
theory. see Chapler 1. Section 75):
11£ '" ,,411~(lil _ ~)Z (7.17)
where /)i is the solubility parameter. or the square TOOl of cohesive energy density. III
this way the classical mixing laws proposed by van der Waals and lhe model for regu-
lar solutions fundamcnlally conform to the same theory of molecular interactions; the
~nges or.pplkalion are lhe !!lime: milllures or.polllr compound!\.

Mixing rule applied to the translation parameter


We have seen [Pl!neloLlx, 1982J that any equation of stale may be corrected using -transla-
tion", For this.. we have said that the result of the equation of Slate before correction was an
inlermcdiate ca1culalion. a "fictitiousn \'Olume. designaled u'. and thOI the volume was
oblained according to equation:
11= II'-C (4.79)
The value of the lranslation. c. is independent of pressure. Under the!iC condilions, for
pure subslanccs tile ca1cul;llion of the liquid-vapor equilibrium. in olher words tile vapor
pressure. is nOI modified.
For lhis para meier. we also need 10 define a mixing law. We shall do lhis in such as way
thai. for mixlures as for pure subslances. the Iranslation does nOI modify the ca1culation of
phase equilibria. For this we have:

,
C = LCil i (K.30)

Indeed. if we calculate the fugacity coefl'icienlS rrom lhe classical equalion:

RTln I~ = fJ'fvi _ RT)dP (5.54)


p~, o~" P
we nOle that lhe parlial volumes arc themselves "lranslaled" from c/. which docs nOI
depend on composition:
v/=iij-c/
such Ihal the fugacilies.. berore and after translation. are relalcd by:

If the liquid-vapor equilibrium condition is verified before translalion:


/;1. <T. P..r) = 1;1' (T. P.y)
lhen il will also be verified after translaTion:
If<T.p..r) = It(T.P.y)
Let us poinl out once again that correction by lranslalion and Ihis definition ror a mix·
ing rule relaling 10 Iranslat ion paramelers arc nol exclusive to equDliollS of Slale deri\'cd
from the van der Waals theory. bUI apply 10 any equat;Of\ of Slate.
283

Thus we obtain tile definitive equation:

RTln 9'; '" J'[-(


..
'") • RT]dV
aNI T;N! v
- RTln Z (8.31)

This equation is applied to the calculaUon of fugacity eoeftkltonlJ eacb lirM Ihal the
equation of'hlle Is uplidl in pressure. and among others. to those illustrated by Equation
(4.50). It is therefore necessary to express the tOlal number of moles H,_ and Ihe lotal vol-
ume V in the equation. Equation 4.50 therefore will be written as:

p. ,;N:c.R;;T. N'.• (8.32)


V-Nib (V - N,b'l) (V - N,brJ
Eqll8lions 8.31 and 8.J2ll1'e independent from the .wlecfed midng mit for Ihe equation
01 state p...lImelers, IIIDd are ..,.. 10 be applied when ~ shall define Ihe mi:dng IIIWlII from
the eJ:~ qWl.D1111es (Sedloo 8.4). We detail below the application in the case of classical
mixing rules.
The mixing rules (Eqs. 8.27 and 8.28) yield the expressions:

N~ II = L.."L..lIlJN/Ni
; j

,
N,b=2b/N,

which we substitute inlO Equation 8.32. We may then calculate the partial derivative of the
pressure as it relates to the number of moles and integrate according to Equation 8.3\.
The resuh is:

8.3.3 Application Range and Results

AtlellSt in prinripko,lhe \'lin der Waals equation 01 stllte is Ilpplied Oldy 10 _.pollU rom·
pounds,.nd lhe~ Is even mo~ of II ~lISOn \'l'hen the dllSSic:al rnixinI naIes that \'l'e h.~'e
defined.~ .,plied lit It. This leaves us with an enormous range. especially petroleum nu-
ids. Whether in the elfploitation of reservoirs or in lhe refining industry. the Soave·Redlich·
Kwong or the Peng-Robinson equations of stale are commonly used. They have been the
subject of numerous modifications.. which we brieny discussed in Chapter 4. but as long as
we limit ourselves to non-polar compounds. the classical mixing laws are the most used.
At lhis level, the main problem is the determinalion of the interaction parameler k y . We
shall return to this point.
The results are generally good. Figure 8.2 (idenlicalto Figure 6.9) shows the equilibrium
diagram for the ethane carbon diolfide system. For this calculation. the value of lhe inler-
action parameter is equal to 0.\3 and independent of temperature. We observe that the
experimental valucs arc well correlated. as are the azeOlrOpic behavior and the area close
284

0.25 D.S 0.75


Mole /nI<;IIQn 01 vIhane

tigUn! ll.2 Liquid·vapor C1Iuilibrium diagram of tile ethane (I)


carbon dioxide (2) system.
ClIk:ulated ClInes. experimental points.

to the critical region. Similarly. Figure 8.3 [l-!urOIl 1'1 Ill.. 19771 shows the critical poinu; locus
for carbon dioxide. hydrogen sulfide. and paraffin hydrocarbon mixtures.
It can be tempting to extend this method to olher compound familia. Asselineau 1" al.
[19781 sho""ed thaI the Soave-Redlich-Kwong method could be applied 10 mixtures of
chlorofluoro-compounds. after determination of the interaction parameter of course.
Figure 8.4 shows thaI this is the case for the CF•. CHFJ mixture. Since this result. many
Olher systems from the same family have been dt:scribed in Ihis way. Goral el ul. [19811
have even applied this method to more polar systems and. according to them. only mix-
tures containing oxygenated compounds had unacc::eptab1e results.
We believe caution is called for in this area. A priori, the dassical mixinll ntles shoukl be
lIpplietl to non·polar sfsiems only. and eilhef aner delermininllihe binary Intet1lction
pllt1lmeter, Of afler hllvi"lll'erirted Ihllt Ihis pal'1ulK'ter may be assumed to be lero.
10 an)' event. a recommendation is in order. The liquid-vapor equilibria of a mixture will
not properly cofTelate Of be predicted if the vapor pressures of the l'Ompooents are not
themselves com:ctlycalculated. Wc have seen that application of the Soave-Redlich-Kwong
or Peng-Robinson equations of state in their original form yields an average error 011 the
8. Applic;>riot> 01 fqu;>riQns 01 Sf'''r It) Mixru,"" 265

"
~
~
~ "
•••
,
c..

.,,, o .,,, .'"


Temperature r'C1

"

• •
.
,..--

-
...~ f"-"'--
, r("

o " ,co
Temoerature I"CI

Figu~ lU Critical points loci for carbon dioxide. pal1lffinl C 1-C ,0 (top)
and hydrogen sulfide. pal1lffin. C , -C. (boltom).
Calclllatcd curves. cxperimcntal points [Huron rr 01.• 1911).
286

5 T .. 283.15K

T~255.4K

;;;
•~
• 3

~•
,
T_224.8K
,

0.25 0.50 0.75


Mole flllCtion 01 CF.

tlJu", ll.4 Liquid·vapor e<jujJjbrium diagrnm of the carbon h,trafluotidt:,


carbon trifluoride system.
Calculated cu",u,expcrimcntal points [A.-lineau I'l ~1.. 19781.

order of I to 2% within the range of temperature between the boiling temperature al atmos-
pheric pressure and the critical temperature. These results worsen considerably at lower
temperall,lres. and we must pay auention to this point for the treatment of systems contain-
ing compounds with low vapor pressure or. of course. compounds other than hydrocarbons.

6.3.4 The Binary Interaction Parameter

In theory, the interaction parameter kij within the calculation for the binary term IIL/

1Ii,j=v'II;./liJ(l-kij) (8.29)
must be determined from the experimental liquid·vapor equilibrium data. It may be neg·
lected in the ease of paraffin mUlures. Elsewhere in the literature we find numerous pub-
288

This reslIh deserves (0 be tempered however. In effect. the preceding calculation ;s the
result of the application ofllle Peng.Robinson equation as it was proposed initially. Under
these conditions. we should nme Illalthe paramelcrs of the pure substances are relatively
uncertain. Methane is found well above its critical temperalUre and the application of the
equations proposed by Soave (expressions 4.43, 4.46. and 4.47). and taken up by Pcng and
Robinson (numerical values from Table 4.5), warrants caution. The same is true for hexa-
decane. for which the reduced temperature is on the other hand very low. The vapor pres-
sure of this compound is poorly predicted by these expressions. For this reason. some
authors [Pedersen et 01.• 19891 have preferred to take the interaction parameter to be 7.ero
for all hydrocarbon binary systems. Yet. it is 10 be observed lhat lhis propositioll is applied
within the framework of a study dedicated 10 reservoir fluids. comple~ mixtures by virtue
of lhe number of componenls. and accompanied by 1I. special treatment for the heaY}' frac-
tions. Additionally. for such mixtures lhe number of components is very high. and the sim-
plifiealion afforded by this hypothesis allows for an appreciable redUClion in calculation
time [Hendricks. 19881. Table 8.2 gives the interaction paramelers recommended by these
authors for biliary systems containing nilrogen.carbon dio~ide. alld hydrogen sulfide,

Table lU
Soave·Redlich· K ,,'oog equalion of Slate:
;meraction panlmelers bel'll'een lIydrOCllrbons and nilrogen.
carbon dioxide. and lIydrogen sulfide [PWcncn e161" 1989]

Component N, CO, H1S


N, 0 0 0
CO, 0 0 0,12
H~ 0 0.12 0
C, 0.02 0.12 0",
C, 0.06 0.15 O.ll7
C, 0.'" 0.15 0.ll7
i·C. 0.'" 0.15 0.06
n-C. 0.'" 0.15 0.06
i.e, 0.'" 0.15 0.06
n,C I 0'" 0.15 006
".c, 0.'" 0.15 0.05

The hydrogen conlaining binary Syslems.. frequently encountered in lhe refinillg indu$-
lry.also pose a difficull problem tllat lias becn lhe subject of $C"eral studies IGrabovski and
Daubert. 197&: Moysan eI 61.. 19831, Firstly. we cannot satisfaClorily describe tile emirely of
llle equilibrium diagram. If we limit oursch'C'S to pressures below 300 bar. it is tllen possible
to obtain valid results. butllle values for lhe interaction parameter are especially lIigh. For
example.k.,; = 0.742 for tile application of tile Soave·Redlicll·Kwong equation to tile hydro-
gen /I·butane binary system at l2O"C. These paramelers are only slightly sensitive to the
nature of the hydrocarbon component. bUl they vary with temperature. Finally. and most
importantly. in opposition to what is generally observed. lhe results are only slighlly sensi-
tive to lhe value of the klJ parameter. Allthcsc observations arc prell}' well explained if we
tllke into accountlhe very high value for the rcdueed temperature of hydrogen (To = 33 K).
The application of Etiuations4.43,4.46. and 4.47 proposed by Soa"e yield a vcry low aurae-
269

lion parameter 8 value for hydrogen. II is therefore the same for the binary parameter li.j
obtained by applying mixing rule 8.29 if the values of kIJ8rc not themselves especially high.
Another. morc general problem eonccrns the variation of the inll:raetioo parameter k LI
with temperature. This variation is often neglected. In any event, it generally remains mod-
craIe. Yel. it needs to be emphasi7.ed that it may have an importance that is not negligible
for the calculation of mixing enthalpy.
The values for the interaction parameter are mOSt often determined by minimiZlltion of
the differences between experimental data for bubble pressure and the resulls or the cal-
culation. Since the data rdative to composition of the vapor phase (dew points) arc more
rare. Ihey are nOI generally taken into consideration. If we are interested in "light-heavy"
binary systems such as the methane hexlIdecane system. the content of "heavy" compound
in the vapor phase is very low (Fig. 8.5). and the relative error for this value could be con-
siderable. and cannot be controlled without experimental data. This fact must be remem-
bered when we seek to predict the retrograde dew pressures of natural gases.. The sensitiv-
ity of this value to the content of heavy component is very high. and often the calculation
is only performed thanks 10 a special adjustment of the interaction parameters. or e'·en of
the nature of the heavy componcnts. We must therefore cmphasiU the value of predictive
methods specific to this problem [Pedersen 1'1 a/.. I989I.

CJ EXAMPLE 8.2
Relationship ber\veen the Henry constant and the binary interaction parameter
It has also been suggested to determine the interaction parameter from the Henry
constant, meaning from gas solubilities in the hydrocarbon solvents. This constant is
defined by equation 5.86:
"'1.2" lim (II),.
,,_O.ll
lim (Pip/i)
>,_11
(5.86)

If.l l -+ O. and if the soh·ent is a pure substance.l z -+ L under the Henry constant
measurement conditions.. the pressure approaches vapor pressure Pf of the solvent.
Equation 8.33 becomes:
P'('b)b
,.. =-In 2 Vj - 2 + .J.(7"_1)
1~, ... 0 RT b ""1
2

+ '" (v.;,;
bzRT('1 -..Ii;
'2) 2 b') In
(l-kd- b
z
and it is understood that the values for Pf and "2" validate the equation of statc and
the liquid-vapor equilibrium equation for the pure solven\.
We see that the Henry constant is ell:plicitly related to the interaction parameter. as
well as to the properties of the solvent at saturation. This method is excellent for cal-
culating the portion of the equilibrium diagram that corresponds to the diluted lones.
but it is not generally possible to predict the diagram as a whole, and the critical wne
in pankular. in this way.
29{) B. AppJ;c~'io" 01 Eqwlionf 01 SlJle /Q MiX/urcs

8.3.5 Alternatives on the Classical Mixing Rules

8.3.5.1 Dependence of the Attraction Parameter on Composition


As we have pointed OUI. the classical mixing rule relating to the attraction parameter:

(K.27)

(8.29)

mllY not be applied to polar mixtures called "asymmetriC. Several modifications have
been proposed thm involve a variation of the interaction parameter with composition.
PanagiOlopoulos and Reid 119861 suggcst a linear variation:
....here ki., = 0 (8.34)
in which we point oul thai in II system with II components. it is not invariant if we inler-
change compounds i and j.
Adachi and Sugie 11986] avoid this deficiency by stating:

klJ '" k~ -of" fl,J{ ~I- z/) where kj; "" kiJ.1jj = -II,J' ki; '" fIJ '" 0 (8.35)
Stryjck and VeTa fi9S6] represcnllhe variation of ktl as:
k<J = ki.!l, + ki.ll (8.36)
For a binary system. these last two equations are equivalent.
Finally. S<:hwaruenlruber and Renon [19891 introduce three parameters per binary:
, nlyl; - "'iii
kiJ = kiJ + liJ hi + lJ) (8.37)
/IIifi + mii,
As Michelsen and Kistenmacher [199Ila1 have shown. these mixing rules have a funda-
mental flaw. For example. if we apply the Adaehi and Sugie model and we consider a ler-
nary mixture having IWO identical components (subscripts 2 and 3) 50 that:
1I~ = IIJ
kiJ = I l3 '" 0.k;3 = kil·lu = / 1,2
the results of the calculation of parameter II relative to the mixture. and therefore any cal-
eulation w;ing the equation or stale, will depend on the relalive proponions of compounds
2 and J. Hence. we cannot apply thl'Sl: models 10 complex mixtures (petroleum fluids) that
often have very similar compounds.
These models pose another problem. i.e, Mdilution M. By applying Equations 8.27, 8.29.
and 8.34 10 8.37. we notice Ihat the terms depending on li or lJ become negligible if the
number of compounds increases substantially. which again, is the case with petroleum mix·
tures.
In liUmllllllry, "-e cannot HI'OClIte tbe lIpplication of these mixing rules dClipite the
indisp.l1able fleJtibility they bring to tHory data coml!lallon. However, we nnte thaI alter_
8. llppIic~lion 01 fqu<tlions 01 Swe 10 M;xlun!s 291

nati~" ....~e ~n propo5ed IMalhiu.I992) lha' elUble us to drCIIIII~enl the den~nd"5


jusl highJilhled. Yel tltey remain enlirely empirial.

8.3.5.2 Application of a Quadratic Mill:ing Rule to the Covolume


Application of a linear mixing law to the covolume:

,
b '='Lb,z; (8.28)

is suggested by the fact that the experimental measurements of density in liquid phase at
high pressure show that excess volume is low. and decreases (in absolute value) as pressure
increases.
Nevertheless. it has been proposed to apply a quadratic mixing rule to the covolume b.
It is similar to the one being used for the allraction parameter.

b ,=,~~biJZ~j (8..38)

U the binary term is calculated using Ihe arithmetic mean of parameter.; b;'1 and bi.i.this
rule is identical to the Hnear combination 8.28. More generally:
bi,/ + b··
b;J'=' 2 N (I -I;,i) (8.39)

introduce!; a second interaction parameter Ii,)' and confer.; added flexibility to the model.
In practice, it ends up that in this way we can acceptably correlate the liquid-vapor equi-
libria of systems wilh polar compounds. such as the acetone water system. Ho.. e~u, ..~
bel"'~.. that CIIulion i!! called for ..·lten app!ylng Ibi!! nde and, in geaenl, it should be
In"oided. If the system in question contains only apolar components. we often run into the
interoorrelation phenomenon of the two parameters kl. l and I./, since several pair.; of val-
ues plot the equilibrium diagram in a more or less equivalent fashion. Their values are
therdore indeterminale. In the presence of polar compounds. this interoorrelation is
minor or does not exist. but sometimes we wind up with a high value for parameter 'I./that
leads to an unrealistic value for excess volume in the dense phase. Indeed. for a dense
phase. at high pressure. for example. or even for a liquid phase far from the criticall;one.
when the vapor pressure of a system does not exceed a rew bars.. the densities arc influ-
enced directly by the value of the covolume. Again. such is the case in Ihe acetone water
~tem for which the optimal values for parameters k;'1 and /1.1 result in an excess volume
close to 20%.
Yel.aomeli_ we ha"e aa:ess to lite excess ~olume val_ Under tltese ronditiom. the
applialion or a quaclntlic: mixi0ll: rule to the ro~olume is justifiecl...... may even pro"e
ne«'SSllry 10 .'iimultaneousty oolT'Clate the equilibrium data with the dell!lity data.
Finally. we note thaI in applications in,'olving the theory of rigid spheres. Equation 8.38
is frequently applied using:

r '"·b'~'
b __ = .; IJ
v 2
which is the equation Ihat corresponds to molecular diameter additivity.
29J

mixing rules are the simplest example. Yel we have secn that the range of application is
limited to apolar systems.
Is It pmslbte 10 combille the INb.nt.~ or the two ,,",thods, booth heltrogeneollS and
homogeM:OII$~

Since we arrive at the same resull.!l using different pathways. i, is probable thaI each
implicitly contains the essential CQIlcepls oflhe olher. We dial! attempt to explain Ihis rela.
tionship using the equations of state derived from the van dcr Waals theory. However, we
nOle that. in general, the principles may be applied to other equations of state.

8.4.1 Calculation of Excess Quantities Using Equations of State:


The Problem of Reference Slates

lei us lake a binary mixture. heptane benzene. for example. al room temperature Dod at
atmospheric pressure. Let us designate the reference stale (pure 5ubslanocs. same condi-
tions of temperature. pressure. and physical state) by the exponent ". The flagged quanti-
ties are for Ihe components; those thaI are not flagged refer to the mixture. By applying the
Soave-Redlich-Kwong melhod. il is possible 10 calculate lhe molar volumes in the liquid
phase for each of the pure components II; and II;. The classical mixing rules may be
applied (a zero value for the interaction parameter is acceplable), and we can lhen calcu-
late the parameters. solve the equation of stale, and obtain molar volume II for a mixture of
composition ll' lz·
Taking the difference. we obtain the excess volume:
, (.
V =1'- VIlI+I':l:
.)

Yet we nOle thaI this equalion implies. as we have just seen. the simultaneous applica-
tion of the equation of state (which is not explicit in volume) to the pure substances. and to
the mixture.
Similarly, we may calculate excess Gibbs energy. To do tltis. note that the fugacity cod-
rtcient is related 10 residual Gibbs energy by the equation:

g(T.P) -g'(T.P) = RTln ~ '" RTln rp (2.38)

for the pure substances as well as for lhe mixlure. Therefore, we may state:

gl.' = RT(ln rp... ~ Ll; In rp:) (5.83)

it being understood that these fugacity coefficients are calculated using Ihe equation:
P(II-b) •
lnfl:-In RT +2-1+ bRTU(v,IVI.r1J (4.57)

If we use the Soave·Rcdlich-Kwong equation. for eaclt of the pure substances we have:

P - ....!!!....... - I{/
- II;-b; vi(vj+b;)
294

P(v;-b;)
In 41:= -In RT

+Z/-\ +
1;'1
--I,
b;RT
and. for the mixture:
RT
".
"",(v.. + b..)

P(v.. -b..) I .. v.. + b..


In f'", '" -In RT +Z",-I+bRTln

Since the temperature, pressure. and composition are given, Ihe preceding equations
lind lhe choice of a mileing rule for parameters a and b allow for lhc calculation of excess
Gibbs energy. Conversely. we know that the excess Gibbs energy data obtained by appli-
calion of a model such as UNIFAC. may allow for the calculation of the attraction param-
eter a of the mixture. and consequently, constitute a mixing law.
In (aet. there are difficullies if we apply this method to mixtures containing compounds
willi very different "olatilities jLermite and Vidal, 1988), which is the general case with the
SOll\'c-Redlich-Kwong or Peng-Robinson equations of state where the predilection range
is the calculation of the liquid·...apor equilibria at high pressure. This problem is related to
the different physical staleS to which the equation of state may be applied. We shall eltplain
this problem using an uample.

o EXAMPLE 8.3
Characterizing the roots of the Soave-Redlich-Kwong equation ofstate

Table 8.3 shows some ellamples of the resolution of the Soa...e·Redlich·Kwong equa-
lion of state applied to the ethane (I) propane (2) miltture at 4O"C and 2S bar. 'llle
detailed results are pro...ided in Appendill4.
The fin>t column of Table 8.3 lislS the mole fraclion of ethane, columns 2.3. and 4 ha...e
the molar "olumc ...alucs. and columns 5. 6. and 7 show the fugacilies for each compo-
nent corresponding to the molar ...olumes. As a fin>t step. we shall analyu the "'alues
pro...ided for molar ...olume. and we note thai they ha ...e been arranged into three dif-
ferent columns. The reason for this is 10 characterize the roots of Ihe equation of state.
According to the parameter ...alues. specifically the temperalure for a pure substance.
the temperature and composition for a mixture. and the pressure. a -cubic" equation
of state may ha...e one or three roots. If there are three roots, their characterization is
not a problem. The smallest root is allributed to the liquid phase. and the largest to the
...apor phase. As for the intemtediate ...alue. it has no ph)"sical significance (it is found
within the zone of mechanical instability since compressibility is positi...e). This is what
occun> for the compositions t l >: 0.34 or 0.54. The intemtediate root was nOI used and
the "liquid" and - ...apor" roolS listed in two separate columns. Howe...er. it may happen
that the equation of state has bUI a single root, e...en if isolherm P(v) shows a mini-
mum and a maximum when the pressure is either greater than the maximum pressure
(the root for the liquid stale). or less than the minimum pressure (...apor slate). This
." ..

1.
C'
I.

iI.iII 1 ~

]IJ>' 1
7
.1-. ~
~

~[ ·1

II :1•.. .1

1 1..

hr nl II
la:-:

1'5

-
tu.
Q..
0

~'

....
m5
Q..
-
0

-'5---f----------,.-----~~~.,....~~~~~~......~~~~~~-..-~~~---I
00 _.:0
oarVQ (em:l· mo·-

't

u
"8 8. ,A,pp!ic;HiorI of f'l""tioos of Sure 10 Mi~r,,~

Yel, having verified the quasi·ideality of lhe mix1tlre and calculated the reference
fugacities. we may calculate the liquid-vapor equilibrium at 4O"C at a pressure of
2S bar using the equations:
ro' ro,
I YI'" I '.T 1

We find lhat XI '" 0.34 and Yt '" 0.53.


We muSt emphasize lhallhis approximate calculation assumes lhal ideality has been
verified. which is not generally the case. Later on (Section 8.5). we introduce general
calculation methods for tile liquid-vapor equilibrium.
We also need to specify lhal the ideality mentioned here is not directly related to the
{acllhal the inleraetion parameter is zero.

8.4.2 Mixing Rules Derived hom


Excess Gibbs Energy at Infinite Pressure

A review of Figure 8.6 shows that at high pressure the behavior of a subcritical rompound
such as propane. or of a supercri(ical rompound such as ethane. and binary mixtures of
both components. tends toward that of 1\ dense fluid. in opposition 10 what is observed at
2.'i bar. For this reason. it has been pTOplI$Cd (Vidal. 1978] that the reference state be
defined as the fluid approaching infinite pressure.
Under these conditions. the molar volume appTOaches a well-defined limit. covolumc b.
The excess volume approaehes zero if we apply Ihe linear mixing law 10 the covolumc. As
for excess Gibbs energy. such as it results from Equation 5.83. il approaches a limit whose
expression is very simple:

(8.40)

Parameter A is characteristic of the applied equation of state. For the Soave-Redlich·


K""ong equation. it is equal to In 2.
If we apply the classical mixing rule. lI'e find:

(8.41)

where: (8,42)

and: (8.43)
8. Application of Cqwriotl:s of Sla'" 10 Mb,w_ 299

The excess Gibbs energy expression at infinite pressure that results is analogous to the
upression from the theory of regular solutions. Indeed. we note that the ratios:

represent volum.:tric fractions at infinite pressure. and that the teons:

~"
;

';
are. by their nature and numerical values. comparable to the solubility parameters. We
have already established this relationship for the energy of mixing at constant density.
We return to expression 8.40. It is very important to note that this equation is inde·
pendent of the mixing rule applied to parameter I.
Illberefore 1110_ us 10 define new mixing rules by preHntlng il In Ihe Conn:
,
~",2ti·M_8 .. (11.44)
b ; bl A

where g~ is an expression for excess Gibbs energy. This expression can be chosen as a
fum;tion of the problem. and the nature of the mixlUre, as we do when we apply a "hetero-
geneous" method such as the Wilson equation. the NRTL models. UNIQUAC, or
UNIFAC Huron and Vidal 11979] ha"e proposed a modification of the NRTL model
where, within the upression for IlXal compositions. the mole fraetioos are replaced by
volume fractions:

(8.45)

This modification has an imponant advantage. We have seen thai the classical mixing
rule is applied to a large number of s)'stcms.lt is therefore desirable to select a mixing rule
which. for such systems. can be reduced to the classical rule thanks to a specific choice of
parameters. Sueh is the case for this modified NRTL rule if we have:
fZ;.; '" 0
and: CIJ '" 8jJ - 8i,j

where: "
8/,j '" - -'- A
';
v'b,bt r::--::-
8j.i=- VSi,j8JJ(I-k lJ )
(b , i bJ)

2
300

, P(MPa)
,
P(MPa)

'.5
,,,
,
,
, 5

'5 •
'.50 r, '.50 10',1,
'" 0.75 10', 0.75

tlpre ll.8 Com:la.iofl of liquid-vapor equilibria for the acetone (1)


...ater (2) system by application of ,he classical milling rule: (doned
cu,."cs) and Equations 8.28. 8.44. and 8.45 (solid nu-.-es.,cxperimen-
tal points) IHuron~' /1t. 1979).

The mixing law defined by Equations 8.44 and 8.45 has been applied with good results
10 many sya.ems containing polar components. Figure 8.8 shows that in the case of an acc-
lone waler system the classical mixing rule yields very poor reaul!$, with the prediction of
an immiscibility lone that, in fact. does not exist, while the new rniJ(ing rule allows us to
correlate the elfperimenllli data up to and within the critical lone. especially by following
the change in the 8zeotropic oom(l'O!ilion.The prediction oftemary liquid-vapor equilibria
from binary data is generally possible, as shown in Table 8.4.
8. II.ppJkdrion oIlqwrionf 01 5w~ 10 MIKr~ 301

Tabl~ lI.A
U"luid-vapor e"luilibria or the acelon~ ""'thanol water 5)'5lem.
Average quadratic devialions for the calculation of bubble temperatures.
EJcperimenral data [Griswold. 1949. 19S2]

11K) Acetone Methanol Acetone Water Methanol Waler Ternary Dala

328.333 0.45
I.,
323-343
m ,.., 0.7
,
0.' OJ
0",
'"
'"
0.75
2 0.'
I>
"'IS
125
'" 0.7

Analogous results may be obtained if the ell:cess Gibbs energy at infinite pressure is
expressed by lhe unmodified NRTL model. or by lhe UNIQUAC model, The correlation
of binary data and study of their dispel1lion is also possible using a Redlich-Kisler model.
II is appropriate. however. to point out the naws in this method:
• We can question the physical significance of a reference state at infinite pressure
since the properties of a nuid can never be measured in this state.
• The mixing rules thus defined, as Slated by the authors. may not verify the quadratic
condition that statistical mechanics imposes on the second virial coefficients. We
Icnow lhat if we apply lhe Soave·Redlich·Kwong or Peng-Robinson equation of state,
lhe second virial coeffICient is expressed by the e'luation:

B=b-- •
RT
such that any mixing rule should respect lhe condilion:

b-~ = L:Ez~-BIJ
RT I i I

where: B(r=(b;- :~) and BjJ=(br :~)


This condition is verified by Ihe classical mUting law. However, it is not verified if the
ell:C(:ss Gibbs energy at infinite pressure is ell:pressed using the NRTL, UNIQUAC. or
UNIFAC model.
In fact. it is at low pressure that Ihis '1uadratic rule is important. and we have never
observed practical consc'lucnces due to Ihis deficiency.
• We can ell:press excess Gibbs energy al infinite pressure using one of the known and
proved models. However.lhe panmde" orthC5C mOOeb mll!ll be determined and we
CIlnnot use tbe l'IIllte!! delermlned from CIcaII Gibbs "nero al low pressure IilKh as
Ibey ha"" beeD assembled in some dalllba$e$IGlIIlebllnl ~t aJ., 198Ol. Indeed. the val·
ues for exct:ss Gibbs energy at infinite pressure and at low pressure are not the same.
From a praClical poinl of view. this is Ihe mt:thod's main disadvantage.
302

8.4.3 Mixing Rules and Excess Functions at Constant Packing Fraction

In light of the remarkable results thai they provide. and also because their expre$ion can
be regarded as complex. we shall develop the5C' methods proposed by Pl!neloull t'I Ill.
I I989J in detail.

8.4.3.1 Formulation of Equations of Slale Derived from


the van der Waals Theory in Terms of Packing fraction
[n gellcral. for given conditions of temperature and pressure. the definition for mixture
quantities is somewhat arbitrary. and its evaluation or interpretation cannot be reduced to
a single bahlnce of intermolecular cohesion energies. This is particularly marked if the sta·
ble physical stale is nOllhe same for the mixture and all its components, permanent gas.
liquid solvent. or liquid solution. for example. A major element concerning the milling
quantity may be the variation of energy for the change of physical state, and we could ade-
quately speak of a "heat of dissolution~. In any formalism concerning mixing quantities, it
is therefore important to carefully select the states of reference such that the model per-
tains to an unambiguous property. In general. the definition of temperature and pressure is
not sufficient to address this criterion. as we have seen. At infinite pressure, any fluid.
whether supcrcritical or not, tcnds toward a dense state, and this limit has been proposed
as a reference. To examine the mixture and its components in the same S13te of molar vol-
ume is unacceptable, The value 40 cmJlmol is acceptable for methane at its boiling temper-
ature at atmospheric prel;5ure. but unaoceptable for a high molecular weight hydrocaroon,
It is therefore appropriate to take into account the natllre of the compollnd. or more
specifically. its actual or molecular volume. Quantities such as the van der Waals \·olume.or
even the critical volume. may be proposed for that purpose.
All of Ihe equations of state derived from the van der Waals theOT}' contain a "repul-
sion" term that depends on the volume and on a parameter related to the actual volume of
the molecules. covolume b.lt is in relation to this parameter thai it seems appropriate to
define the reference vol lime when .....e study these models.
By definition. in this sllldy we state that packing fraction (-reduccd dcnsity. density-) is
the ratio of the covolume to the molar volume:
b
II '" - (8.46)
"
When the packing fraction is the same for the mixture and its components. they have an
eqllal proportion of-free vollime relative to their actual volume.
M

The equations of state that we are considering are fOllnd in an especially simple form as
a function of this variable. So. if .....e state:

(8.47)

the van der Waals equation becomes:


• 1
Zo---a,
1- ,
303

and the more general Equation 4.50:


• 1 1
Z. -I_-n'r - a" (;;I-;"'';;--';:~
(I
WI) -lJr~
(8.48)

This observation may be generalized 10 all the equations of stale derived from the VBn
dec Waals theory. which can be wnnen in the form:
1
Z. - - - 01/11'<11) (8.49)
1- ,

For the van dec Waals. Soave-Redlich-Kwong. and Peng-Robinson equations. (l is inde-
pendent of packing fraction. and depends only on temperature and. for a mhuure. oompo-
silion. The \I" function itself depends only on the packing fraction and lhe chosen equation
of stale (via ttle intermediary of constants '1_ '2)'

8.4.3.2 Calculation of the Helmholtz Energy A


For an equation of state thal is applicable to liquid and vapor states (and explicit for pres-
sure). the corresponding characteristic function is Helmholtz energy, and not Gibbs
energy.
If N is the number of moles. and A and V the corresponding Helmholtz energy and vol·
ume. we know that. at a constant temperature and numbcr of moles:
NZRT
dAT,,-PdV=- V dV

Accounting for the definition of packing fraction. we have::

b Nb dV dll
11"-"'-
, V "d -V
. - -,
at COIlstanl numbcr of moles. such that:

dA T ", ,
NZRT
dry

For the ideal gas (denoted by superscript I). the compressibility factor is equal to I. and:
• NRT
dAr'" - - d ,,
The variation of residual Helmholtz energy with packing fraetion is therefore equal to:

d(A-A')," NRT(Z-I)dry
,
If II ..... O. then A-A' ..... O. and we derive:

A-A':NRT
f,
~(Z-1)
, dll
8. IIppIkarion 01 fqwriom 01 Sf,,,,, 10 Mixtures 305

Therdore. we can calculate the Helmholtz energy of milling at constant temperature


and packing fraction, defined by:

Q!of (T,:c. 11) '" Q (T,:t, 11) - LZ;<J;( T, 11)


We find:

The first term corresponds to the miJuure in the ideal gas state. However. neither the
pressure nor the molar volume arc constant:
b
."
v- '" bj v'" -

"
In order to calculate this term, we use a reference stale defined by the value for molar
volume. "0. at the same lemperature. of OOUI1iC. [f ar
stands for the Helmholtz energy of
the comp<ments, and aO for that of the mixture. both in the ideal gas state. in this reference
state:
v- b_
a r(T,I1) '" aj- RTln -'- '" oi- RTln - ' -
VO 11 .,°
and: a'('{,I1) '" 0°- RTln -" = 0° - RTln-
b
VO .,° 11
therefore:

0"

Furthermore, we know that for an ideal mixture of ideal ga$C$ aehieved at constant vol-
ume (or prcssure):

such that we obtain:

a.ll(T,l. q) '" RT[ Ll; [n l; + Ll; In ~ - (a: - v;a,{)] (8.54)

We note that this expression in broken down into three terms. The finil represents the
ideal mixture, the second has been introduced for the ca[culation of the Helmholtz energy
of mixing at CONIhutt padr;i,,& fT1ldlon and is identical to the expression for the Flory com-
binatorial term. and the third is sometimes eharacteri2:ed as "residual", 11 refers 10 the
attraction terms that exist in the equation of state:

a":., (T,l,I1) = -RT(~ - LlM) (8.5S)

This term may therefore be calculated within the scope of the initial hypothesis. thc
equation of Slate defined for the mixture and its components.
306

Definition of the equation using the attraction term aZ:.


Let us look III the case "'·....re for elldJ tomponC'nl the equation of slale (terms b/. o:,'~)
is defined. In addition, let lIS acIoplII linellf mixinalllw for lite col'olume:

b=~b,z;
, (8.28)

ffo..-e\"l~r.lhe \-alut'S for Q.nd ~ relating to the mixture tor I'lIIlher their product) are ftOl
defined.
We shall define the expression for the function II~, as a function of temperature. pack-
ing fraction. and composition. The product a~ will be derived by applying Equation 8.55 in
the form:

_ £,za ~.- ""~""(i'i',·","1


-" (8.56)
I " RT
"'
as well as the product a"by application of Equation (8.SI):

a•• ('<<><I)
(11/ 1.'''i
'L"',('<)
dlJ
'
__,
RT
("":,(''''1)
dl'j
T 1."'1
(857)

The fllndioo a:' must !i.IItisfy «,rtain cunditions. It is analogous to an excess function.
and approaches 0 if the mixture reduces 10 a pure substance (,l', ..... I). or if the packing
fraction approaches 7.ero.
II depends on temperature. packing fraction, and composition. It is possible to have
these last two variables intervene simultaneously by defining "DOLCH. or density dept'"d·
til/local compositions. However. from a practical point of view. we prefer to dissociate the
effects of composition and packing fraction by stating:

(8.58)

1(1l) is a function that depends only on packing fraction. and approaches :lero at the
same time as this variable, Gf:(T, z) depends only on tempcraltJre and composition. and
cancels itself oul for "1 "" 1 (pure substance). 11 seems reasonable to express dependence of
the attraction term with composition. using an excess Gibbs energy mood
The preceding equations show that the teTTflS ~ and ay/llfe related, It is necessary to
point out an imponant special case. since it in fact constitutes the rule: for all components. we
choose the same equation of state (the same functions Ifl or~. regardless of I). and for this
equation of state the function ~ depends on packing ftaction only. In this case. and with no
other infonnation. it is logical to apply this same function 10 the expression 1(1l). By Slating;

(8.59)

Equation 8.56 becomes:

p'
307

that is 10 say. afler eliminating function ¢


¢(1:t)
a= Lz;a;-
RT W)
• _ '" a; qt'(T.z)
(8.60)
or: j) - ",-Zi b{ - ~(l)

and we can easily nOlice. in Ihis case, the identity Ihal exists with the usc of excess Gibbs
energy at infinite pressure (Eq. 8.44).

8.4.3.4 Results: Abdoul Group Contributions Method


or course. we may apply this ml'lhod to the correlation of binary data for polar systems
[termite and Vidal. 19881, using the UNIQUAC model, for example, for representing the
G£(T,x) funclion. The resuhs are analogous to those obtained using excess Gibbs energy at
infinite pressure and the modified NRTL model. II is mOTc illlcresting to look al the
method of group contributions proposed by Abdoul 1'1 ul. 119911.
The choice of an exces.~ function model at work in Equation 8.60 and using group
ooniributiOliS is not necessarily a simple one. AI first glance. the UNIFAC [Fredenslund
"/ al.• 1977J and the Lennite and Vidal [19921 or ASOG [Kojima andTochigi. 197';1] models
come to mind. Yel. none of thcse: models reduces to the classical mixing law. whose: validity
is well kno....n in the case of apolar systems.. Furthermore. for such systems the t....o interac-
tion parameters between groups are strongly correlated, and due to this fact. poorly deter·
mined. The importance given here to apolar systems is in no way exaggerated. They pr()-
vide the ground....ork for our databases and the pr.actical application of calculation meth·
ods for phase equilibria al high pressure.
Since the classical mixing rule is conveniently applied to such systems.. it is appropriate
to analyze it in teons of excess functions.. Equations 8.41 to 8.43 are absolulely c<Juivah:nt
to the classical mixing law [Vidal. 1978: P~neloux. 1989J. Adjusting the experimental data
or predicting the binary parameters kl.Jor ElJis therefore the same. but the Ell parameters
are directly related 10 excess Helmholtz energy. It is therdore this parameter thai "'e shall
express by group contributions.. Abdoul 1:1 al. [19911 applies a modification of thl:
Guggenheim reticular model 10 it. and as firsl approximation Slates:

(8.61)

....here: EI.J(T) = -~2 LL(a


k I
u - a·. t ) (au - aj,llA.v(T)
I
(8.62)

where av
is the proportion of groups k in component i, The interactions bet....een groups.
At,l' in principle depend on lemperature. and their values are determined from a large
experimental database: of liquid-vapor equilibria at low pressure, high pressure, and healS
of mixing. The components considered include nitrogen. melhane. ethane. carbon dioxide.
and hydrogen sulfide, each of which make up a distinct group. and the paraffin family. rep-
resented by Ihree groups. plus cyclanes and aromatics. for a 10lal of 11 groups.. However, il
308

was observed that it is necessary 10 aCCOUIIl for a "chain length effect" with the addition of
a second empirical term. Ultimately we ha\'c:

~-""z.·'I ... -~bL""tP(/)£


b LIb; 2 /7' /I,J
+1:
"-;!
(8.63)

where £z is determined from the principal hydrocarbon chain lengths:


£1= E...(T)LLZ/l/('i-9 1 (8.64)
, I

The resulls arc of remarkable precision. Figure 8.9 illustrates the distribution of errors
al bubble pressure as a function of the number of systems in question.

Flpn: 8.9 Application of the Abdoul method 10 the prediction of


liquid·~apo. equilibria for hydr<><;:arbon systems under pr«l!iurc.
Di51Tibulioo of tile errors COfloxrning bubble prnllurc.

Essentially. this model contains two hypotheses. First. the validity of the classical mixing
rule corrected by the chain length term. the importance of which is generally low. Then.
most importantly. the possibility of applying a group contributions method to the inter-
molecular interaction parameter EW
We can altcmplloextend lhis method to systems other than hydrocarbon mixtures pro-
vided, however, that for such systems. the classical milling rule is applkablc.
This has been done IFransson.I993J for mixtures containing chloronuoro-hydrocarboll$.
It is known IAssclincau er al., 19781 that the Soave method combined with the classical mix-
ing rule allows us to calculate lhe liquid-vapor equilibria of sucb mixtures. This shows that
for each system it is possible to dclermine an interaction parameler value klJ or EiJ such
that the representation of the equilibria is acceptable. This EIJ parameter is predicted by
the expression 8.62. and we added the groups below to those defined by Abdoul el al.:
'"
'00 - , - - - - - - - - - - - - ,

'" ••
,,
,
,,
,
,,•
,
,,
• •

-- --
, 0.25 0.5 0.75 ,
Mole I,action ol acelOO8

F'lguR LIe Prediction of the equilibrium diagram for the tl<:Clone (I)
"·hen..,, (2) 1)"'lem using the MHV2 mdhod. T .. 323.15 K.

We may ha\'c difficulties if some of the components are found at the limits of Ihe value
mngt for a within ""hich we applied a second degree polynomial expression to the q(a)
expression. II may therefore be preferable to use another q(o:) expression. such as the one
suggested by Soll"C [19921.
or course. if we arc talking about liquid-vapor equilibria under pressure. the s)'stem
probably contains some light components (methane. elhane. carbon dioxide. etc.). Ii is still
possible to apply an excess Gibbs energy model. hut the parameters must be determined
for binary S)'Slcms containing such oomponenl5. because Ihis oould nOI have been accom-
plished by a "heterogelleous" method. Similarly. with equilibria under pressure. tempera-
ture can be significantly highcr than the range for which the paramelers in the database
have been pUblished. We are now extrapolating. and Ihe results may be wor-;e.
It is of course very usual to ClI"preSli excess Gibbs energy using a group contributiortS
model. Dahl ellJ/.ll990a. b. cl have done jusllhat using the UNIFAC model modified by
Larsen [1987]. Again. in this case the results liTe reliable. even al high temperature, lIS
shown in Figure 8.11. This figure shows the acetone \\'au.'r equilibrium diagram up 10 the
critical7.0nc. We may compare the results 10 Ihose or Figure 8.8, which were obtained using
excess Gibbs energy al infinite pressure. lhc interaction parameters of the light com·
pounds and atomic groups were determined. and gas solubililies were predicted for
s~lems composed of hydrogen, carbon monoxide, mNhane. carbon dioxide, hydrogen
sulfide, and water. The MHV2 model was also applied to the liquid-liquid equilibria pre-
313

, T.523K

• • • • • EXPER
MHV'
~
~ • r. 473 K

J •
, T. 423 K

0+-------,--------1
o ,
flIu~ III I Pfl-dietion of liquid-vapor equilibria for the acelone (I)
""'lllcr (2) system using the MHV2 melhod [Dahl cf "1.• 199(8).

diction in the critical zone [Dahl et al.. 1992a]. and uhimaleJy extended to solutions
containing electrolytes IDahl el ill.• 1mb].
In summary, the MHVl method ~ bltSed on II dcMt: reference stille, but .t zero p....s-
sure. whidl .lIoWl! for Ihe use of pre"IOllSly defined models (expressions lind Pll....meten).
and on the more specific appliaotlon of Ihe UNIFAC mod...lth.1 provides 10 lIthe IId...n-
lagts of the group contributiolls methods.

8.4.5 The Wong and Sandler Method [19921

The mdhod pro~ by Wong et al. 11992 II lind bl.1I11ellsf in prinriple.IIIWWll us 10 soh"c
'''0 problemslhlll"~hllo"c already disnlssed. namely thOR ronccmlnllhe ru~ of eJ(<<lJ'!j
Gibbs energy derived III innn!I" prY$Jlu"" Like the MHV2 method. it may use Ihe models
(eJlpressions and parameter values) that already exist. In addition. it retains the quadmtic
variation of the serond vinal coefficient, This method is based primarily on the expression
for excess Helmholtz energy at given pressure and temperature.
The residual Helmholtz energy is expressed by til... equation:
P(II-bj .. .,+b
a-u'=-RTln - -In-- (8.78)
RT h "
314

Applying this expression to the mixture and its components 8t the same pressure and tem-
perature. we derive from it theexcus Helmholtz energy althe given pfC$ure and temperature:

a,___ RT[' n P(v-lJ) -"'z/


"" , n P(Ii;-b;)]
RT i RT
(8.79)
a II-+b "" _/
- [ -In - - - ,,;..::;-In
b" Ib,
.....hich differs from excess Gibbs energy only by the tenn pvL:
/l~'=gE_PIi£

At infinite pressure. the limit of excns Helmholtz energy is equal to:

b ",' ''')
, =- ('--"",::/-
0 .. 1112 (8.80)
b·,

(8.81)

Furthermore. if 8 is the second virial coefficient of the mixture related 10 the parame-
ters of the equIlion of stille by equation:

8",b- -
, 8
-:1--
,
(8.82)
RT b bRT

we derive: (8.83)

The second virial coefficient is calculated using a quadratic mixing rule:

B= L, 2A,ft
I
rtj (5.11)

8 ..1+ 81J
where: BiJ= 2 (I-Iv) (8.84)

and (see Chapler 4): (4.61)

such thaI Equation 8.83 becomes:

b. (8.85)

If we sel«t an e~cess Helmholtz energy modclat infinite pressure. once the parameters
of the expression and the 1.1 parameter are known. parameter b ror the mixture is obtained
by application or equation 8.SS. and parameter II is obtllined by Equation 8.81.
315

However, it has been observed that if we calculate the ucess Helmholtz energy for a
dense phase using Equation 8,79 al increasing pressures. this property varied lillie wilh
pressure. By denoting the excess Helmholtz energy as a~ for the dense phase close to
atmospheric pressure, we can Slale:

The excess HclmhollZcnergy a~ is calculated using any available model (expression and
parameterli),such as those discussed in the previously mentioned database from Gmehling
fit aL [19801. These databases must provide the value for g~. and for the fq parameter such
thai the excess Gibbs energy. at low pressure and for the dense phase calculated by the
equation of Slllte, is as close aJl possible to the excess Gibbs energy calculated by lhe model,
This proo::cdure is completely predictive when we study a system for which the parame-
ters of an tlfcess Gibbs energy model are available. We may also apply the UNIFAC model
[Orbey ct 11/•• 1993 J.
The authors have applied the van Laar and the NRTL models llnd obtained good
results. even wlKn extrapolating the calculations beyond the range of temperature for
which the parameters of the model were determined. Of course. in the presence of light
components,as for the MHV2 model. all model parameters must be deterrnined since they
are not found in the literature.
Table 8.5 shows some of the results obtained by using this model.

Table 8.5
Prediclion of liquid-vapor equilibria using the Woog
and Sandlcr m<:lhod [Hernandez GardlJZll. 1993]

System T(K) liP ('li,) 0,


Methanol·benzene
Ao::etoo-water
Acetone·methanol
373-493
373-523
373-473
,'.M...
2.45 0.02
0."
0.021
Water-methanol 373-523
Walcr-ethanol
Water-propanol
423-623
423·573
'"
2.22
3.13
0.012
0.012
O.on

Note llult lhe mixing rule relating to the rovolume is no longer liJteH. Due 10 Ibis fad, It
may y~ld unrealDtie \'IlluClII for nees5 volume in Ihe detue phase, and profoundly altn the
innuence of pl'Clll5ure on phase equilibria.

8.4.6 Advantages and Disadvantages of Mixing Laws


Derived from Models and Excess Functions

The relationship established between the heterogeneous and homogeneous methods has
proved advantageous. The calculation of phase equilibria under pressure using the equa-
tions of state may thus be extended to mixtures containing polar components. The group
contributions methods may be applied to the equations of state. where they reinforce their
predictive ability.
316

We h:ave discussed four alternatives. We must make a special CllSC for the Abdoul
method thai concerns only mixllIres of non-polar tOIIlpounds. bUI which. for these syMems,
seems 10 os 10 be the mOSt precise.
II would be i.l1crCSling to make an extensive comp:arison of the MHV2 method lind the
method proposed by Wong and Sandler since they arc both characterized by the possibil-
ity of using the models and paramctcl'1l thai ha"c already been determined from equilib-
rium data 31 low pressure. These methods have been investigated by Knudsen [1992).
Hernandez GarduUl (19931. and Huang and Sandler 11993]. The MHV2 method is more
developed. and combined with the UNI.FAC model. has undeniable merits..
This d/)t"fj nol Olellll IhlllillU Ihl:' prublell1li hllve been rli'S<)lvl'd. We would like 10 mention
11'.'0 problems llial do nOl. in our cstimation.currently ha"c an acceptable solution.
Thc firsl hIlS 10 do ..ilh milllu,," oonlllining molecule!; of "cry diffe~nt silt'!;. 'rlle
results deterior,tle as this difference increases. For example. such is the case with methane
paraffin systems. Here we have a range similar to polymer solutions. The difficulties are
possibly due to an erroneous evaluation of thc combinatorialtcrm and the "free volumc"
term (sec Chapter II) in the understanding of excess quantities or the mixing rulcs.
The second eumple ill Ihree-pllaR flIuilibria. and in parlicular. equilibria between
methanol and the light hydrocarbons. methane. ethane. or propane. Figure 8.12 shows the
equilibrium diagrams for systems made up of methane and either ethane or ethylene
[Ma and Kohn. 1964: Zeck and Knapp. 19861. We notice that. within a temperature range
dose to the critical temperature of th" hydrocarbon. th"re is a three-phase equilibrium
7.one.ln this instance. no method can truly account for thc experimental data in a slttisfac·
tory fashion. We must add that this problem is an important one from an application point
of view since mt:tltanol is used as a solvent for tlte treatment of natural gllSl.'S by serving as
an anti-hydrate additive. The problem is fUrlher complicated by the presence of water.

8.5 CALCULATION OF LIQUID-VAPOR EQUILIBRIA

Liquid-vapor equilibria under pressure arc mOSt generally calculated using cquatioll.'i of
statc. 'll1e parameters involved in the mixing rules are determined using experimental
equilibrium data, In the preceding diSl.:ussion. we considered this probll"m resolved.
FiI'$I. we go back to the calculation principles and the equations related to the model,
which must be simultaneously verified using the equations or state derived from the theory
of ,'jill der Waals as an example. The general principles, however. may be easily applied to
other equations of stmc,
The calculation procedure is iterative. At each step. wc use values for temperature T.
pressure P. and compositions for phases in equilibrium x,. and )'1' These values may either
be gi"en in the problem definition. they may he the result or the previous iteration or of
the initiali13tion procedure.
From tlte temperature we can calculate the parameters for the components of mixlure
II,;;. Dnd b" as well as the binary terms "I,j by application of Equation 8.29:

"oJ '" V"LJ"U (I - Ii,) where kM • klJ (8,29)


318

The mixing laws aTt then applied [0 the liquid phase of composition xi_ for example:

III. =~L.;/Ix, (8.27)


, J '

b L = Lb/x/ (8.28)

if we 3rC dealing with the classical mixing laws. We IhclillOlve the equation of stale:
RT .'.
P", I/I._b[- (v L _b L'j)(III._b L'2) {4.50}

If this equlliion has three rOOIs., we consider only the smallest one. If we find only one
rOOl, we must check. that it ool'fesponds to a dense phase.
Finally. we calculate the fugacities:
P(vl._b L ) b
Inrp/L=_ln RT +b~(ZI'-I)

(8.]3)

The preceding steps are repeated for the calculation of fugacity coefficients in the vapor
phase. We apply the mixing laws with compositions }II:

(8.27)

(8.28)

and solve for the equation of Slate:


RT ltv
p= VV bi' - (v¥ bV,J(IIV_bV,z) ('-.50)
If we find three rools. we choose Ihe largest one. If there is only one rool. we check that
it corresponds to a vapor phase.
The expression for the fugacity coefficients is then:
v P(vV_b V) b l v
Inrpl =-In RT +j;V(Z-1)

(8.33)

The equilibrium condition is ultimately wriuen as:


rpILXj=rp,vYI (886)
[t seems that the sequence of operations is simple and that it is fundamentally based on
initialization of missing quantities. and on the process that perpetuates ;tenttion until
condition 8.86 is verified.

p'
8. loppIic~/ion of [qwriom 01 Sidle !O Mix/Ufe! 319

In fact. the calculation of liquid-vapor equilibria under pressure presents certain diffi-
culties due to:
• the proximity of thc critical zone:
• the presence of the retrograde condensation region:
• the rather small differences between the proJlCrties of the liquid phase and the prop-
erties of the vapor phase:
• the possible continuity between ~liquid-liquid" equilibria and "liquid-vapor" equilibria.
Therefore, it happens occasionally that a calculation yields the "trivial" solution.accord-
ing to which the two phases in equilibrium are identical. and the system is mistakenly
located outside of the two-phase coexistence zone. This problem is easy to understand
when the resolution for the equation of state for eithcr one or both of the phases has only
one root.
The usual methods, the SCH:alled substitution methods, currently applied in the calcula-
tion of liquid-vapor equilibria at low pressure. may be used in many cases. Each single step
is rapid. but we observe that their convergence may be very slow.
The calculation algorithms Ilave been the subject of several studies. A review of these
studies was done by Heidemann II983J and, more recently. by Michelsen IJmJ and
ptneloux II992J. We shall not go into the details of tllese sllIdies but shall limit oursel,'cs to
stating the principle of the most commonly used methods.

8.5.1 Newton Method

If a system is known by the qualltity of each of its components, the whole of its properties
may be detennined if we know the temperature. prcssure. the quantity (number of moles)
of eacll of tile phases present. and the composition (mole fractions) of these phases. For a
two-phase state. there are therefore 2N + 4 quantities. For each component. we have equa-
tions for material balance and cquilibrium conditions. The sum of the mole fractions in
each phase is equal to one. We hence have 2N + 2 equatiolls. The problem is therefore
defined as soon as we have two definite quantities selected from among those we lIave dis-
cussed. or from among the Ihcrmodynamic properties (total volume, enthalpy. etc.). For
example. if these given quantities are temperature r" and the total volume V":
r~ r"
and: NLvL-+-N"vv:V"
where v L and v V arc tile values for molar volume in liquid and vapor phase. calculated
from the equation of state.
These two constraint equations complement the problem. made up of a system of
2N -+- 4 equations (non-linear) and 2N -+- 4 unknowns. Asselineau 1:1 al. [19791 proposed
applying the Newton method to solve it. The Jacobian matrix must therefore be known.
This matrix is made up of the partial derivatives of eacll of thc functions defined by the
equations that we have just listed with respect to the variables. and in particular. the fugac-
ities with respect to temperature. pressure, and composition. From one type of problem to
the next. and according to the problem data. only the final two lines of tile system change.
It is obvioU:l that the system thus formed may be simplified in many cases.
! 11

1llne.ell1

1m

1
R· '
'. , R

- I
I

]n

th_

h It
, .--
I J

-0.

I',

au
324 8. AppIic.. rion oj fqu;oliom 01 S1.. w IV Mi~I"""

CONCLUSION

CLlrrCll1 "~corks dedicated 10 the equations of state and mi~ing la"'1; attest both to their
practical imporlancc and the subject's Iheorc:lical value. as well as to the shortcomings of
the methods most oftc" employed.
'l'he calculations used to evaluate the potential of all oil or nalUral gas deposit and to
improve exploitation. apply the equations of state derived from the van dcr Waals theory.
The same is true for refining processes. and it has even been proposed that the Pcng-
Robinson equation of state be lIsed \0 determine methanol synthesis equilibria (see
Chapler 13).
The representation of all thermodynamic properties. phase equilibria. densities. heat
capacities-CIC.. using a single model is a seductive thought. and presents a challenge fOT the
"inventor" of such models.
However. as pointed out by Prausnit1" the "interaction p<lrametcr". or the corrective
term necessary for the mixing laws. is evidence of our lack of understanding. 111e exten·
sions sanctioned with the introduction of the concept of excess function fall far short of
solving all the problems.
The prediction of liquid-liquid or three·phase equilibria pushes the limits of our models.
The calculation of these equilibria also requires particUlarly robust algorithms. No mailer
how refined these algorithms are today. we must be aware thattherc is risk of error in such
cases. II is no easy task to combine swiftness with safety. However. these twO qualities are
sought after when we study a comptex operation such as the exploitation of a reservoir. a
polyphasic chemical reactor. or if we are interested in dynamic simulation of chemical
engineering operations.

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