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
J
Predicting Thermodynamic Properties of Pure Substances.
General Prindples. CorrespondJng States.
Group Contributions
•
Equlllions of Sllite
CbMraderizatjOD
• or Mixtures
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
•
Application of Equations of State '0 Mixtures.
Calculation of UquidVapor Equilibria Under Pressure
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
8.4.2 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
9
LiquidLiquid and LiquidLiquidVapor Equilibria
III
fluidSolid Equilibria. Crystallization. Hydnltes
11
Polymer SolatioM and AUoys
11.
MuUicomponent Mis:lures
Chemin' Reactions
AppelldiJi 1
Datahase 435
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
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
1.1 DEFINITIONS
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 steadystate 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·
ariesA 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.
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 socalled 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.
p'
4
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.
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:
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:
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
1.2.3.1 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)
At this point. it is appropriate to consider a few particular cases that colTcspond to this
simplified ...ersion of the firsllaw.
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)
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>
We say lhal an open system is in a steadystale 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 steadystate 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.
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 'ndepth 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)
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)
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",TdSPdV (1.230)
I f>
and: dS= dU+ dV (1.24a)
T T
1111:$1: equalions generally perlain 10 one mole:
dll=TdsPd" (l.23b)
1 P
w .. d"+d,, (l.24b)
T T
Of COUI"SC. if Olhcr forms of energy transfer inlervene (for example. due 10 Ihe existence
of an elcclromotive force). il is appropriate 10 take them into accounl and we would wrile:
(1.25)
Wilhin lhC$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
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
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, 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).
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).
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' .. dUTdS
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(UTS)rv or W'''A(UTS)
at constant temperature and volume
The function:
A=UTS (1.29)
is called the Helmholtz energy.
13
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
, <orr
',,7....,~ ' .•l.!.', ~~< ' . .' i' ...f /
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 ,
uatl0n~
.
(f
h'
Th,_ ~,
!l!i,"1IiC'CS'
OLI, '.•
, 'h,
,
I JU
~l au
16
r
MI"Q+W (1.16)
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 +80W6e 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 . Kl) 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)( Iol~ 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
4U=W"tW'+Q=S3JkJ
AA"'<1G A(PV)=766kJ
The entropy variation is derived from the values of Ii./{ and flG:
T." t.2
Variation of lhermodynamic pr~r1ies. heal e~changes.
and work during lhe o~;dalion of mel hanoI
'".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
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""TdSPdV (1.23a)
Taking into account the dcfinition of Helmhohz energy and Gibbs energy (Eqs. 1.29
and 1.33) one may wrile:
dA ",,PdVSdT (1.44a)
dG=VdPSdT (1.450)
or for one mole: da",,Pdl1sdT (l.44b)
dg=vdPsdT (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:
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
" (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.$3)
,::'
T
(';) .If. " (1.54)
aT.. T
,'T ,
,G) ,G
(2
aT
=_~ T
=H (1.55)
I' T
,'T ,
Their proof is very simple. For example. for the second equation we can write:
21
They should come close 10 a very common graphical representation in physical chem
istry: we usc the variation of the logarithm of a value such as vapor pressure. the
liquid/vapor equilibrium constant, the solubility of a gas. the equilibrium constanl of a
chemical reaction. or the Talt constant. as a function of the inverse of absolute tempera
HIre. In fact. for each of these valuC5lhcrc exists an equation relating it 10 the variation of
Gibbs energy.l!.G. accompanying the described phenomenon: Gibbs energy of condensa
tion. of reaclion. or of formation of an activated complex. tiC. and the graphical represcn
talion. allows us 10 obtain the variation of enthalpy. MI, of this same phenomenon.
This enthalpy variation itself is most frequently only slightly sensitive \0 temperature.
and Ihe graph obtained is linear.
If the variation of temperature causes a phase change or a cllemical reaction. it is then
no longer JlO5Sible to state thai dU v = C v dT or dH p = C p dT and il is neassary (0 intro
duce Ihe ~Ialen(' heat associated with Ihis phase change or wilh the heal of reaclion. On
the other hand we may, willl the help of Equations 1.51 or 1.55. calculate the variation of
the heat of reaction or the Gibbs encrgy of reaction wilh the temperature. while pressure
remains constant, provided that tile systems fanned by (I) the reactan!$, 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:
CVdT+T(aP)
fJT v fJT
(av) dT=dHp=CpdT
f'
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
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:
and the internal energy. enthalpy. and Gibbs energy are obtained immediately:
p'
23
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.
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.
R. 1.987 CIII· molI. K I .. 83.145 bllr·anJ·mol l • IeI. 82.058 111m ·anJ • molI·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 liquidvapor 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:
,'(T P')
P' dT (1.74)
T
and at pressure P:
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 molI. Kl for noble gascs.and 7 cal, molI. 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:
[
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. nbutane.
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. 169179.
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•.111797.
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 liquidvapor 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.
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)· molI)
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}
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 · molI, 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,,; : Iwopha5e envelope: *:critical point.
Pl'cssure. .'olul"lX.tcmP'C'raHlrC diag11lm for cillane.
0.75
I;:
~O.5
,•
~ c
   ,
o
" Pressure (MPe)
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
...'"
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 "twophase 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.
",,
.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.
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
dP" .l"v.,,_.I"I."
or. dT • 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 blllejUSC 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.
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
. 1r,,"'I
3 • , ,
1 OOCVT(K)
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 OausiusQapeyron 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)
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.
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 + [(ad)(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.
Ruzicka and Mayer [19941 recommend il for representing the vapor pressures of hydro
carbons.
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·rIr~. 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:    : twophase 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 Mlwophase enve
lope~ on Ihis diagram. It corresponds. poirll by point, to the twophase 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 twophase 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).
,
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, motI. 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 temperHure al atmospheric pressureIt must be remembered thaI
the Ttouton equation is nOI applied to Iluloassociatcd romponel1ts.
Equation (2.14) may be wrinen as:
"""
",
 (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'
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:
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
dT = T(vV.rs_ II L") (2.8)
and thus:
We end up with:
!JJr" '" T(v I:"  v t ..) c::;'" 353.24(28041  95.6).10 6 .3120.=0 30794 J. molI
This result is "ery close to the clCperimenlal value (30.760 J . molI). 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 . molI with an error in Q.cess of 3.7%.
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:
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
(iJp"') =,,_r(a,,)
T ilT f'
(1.51)
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:
( RT)(
,,' 7:1" .. ;;,11 II' T,P.II"= RT)
P
To arrive alttle residual leTm for enthalpy, it suffices 10 remember the equations:
h=u+/'II and "':lI'+RT Ihatis(hh')=(lI_u')+PI1_RT
We then obtain the equation:
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 prtssure at constant temperature is
equal 10 the volume:
(IA5)
We therefore write:
(2.30)
' ~
,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( ;; LpJ dv + PoJ  NT (2.29)
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
PTJ dl'RTln+PvRT
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.
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)
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):
This last term is generally low compared to the preceding terms, in particular compared
10 the heal of vaporization.
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:
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)
Table 2..,
Calculation of th" fugltcity of ethane in v.. pot phase al 25"C
,. "
,, NTiP
f}';l" • f
(MP.. ) (~n\l'n\olIl (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
23l ""
"'''
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
T.blelIO
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
(2.53)
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:
T cOP
5=sO(To.P")+
I ToT
...!dTRln+(ss'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 lhrle
vapour pressurcc C<Jualions. J. Ch~m. Thunrod,.,u,mia., 10.165·169.
Ambrose: 0 (1911\b)The rone1alion and estimation of"apour presIIures.II.A new proa:dure foresti·
malion and eKlrapolalion.J. Ch~m. ThumodYmlmil".J, 10.165169.
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, 12.811819.
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. 419483.
King MB. AINanar 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. 10031011.
Lewis ON. Randall M (1923) TI'umod,.,ra"'ia 'JIId ,h. Frte En.rgy of Ch.micol Subslam"'s.
McGrawHili 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..83.2114212J.
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,
23.139.
YaWll CL, Yang HC (1989) 10 estimate vapor pressure easily./I}"droca,lJon PrrKQsillg.68.( 1O).65fl8.
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.I3631367J.
• 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
(3.2)
• Dispersion forces; we must take inlO account lhe cohesion forces thal exist between
nonpolar 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 nonpolar 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 ~ ~
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 MOnlcCarlo method or molecular dynamics.
The MonteCarlo 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.
(3.4)
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 (cp4)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
Thus we oblain:
"_(ToP)
RY
.f'ol'iJT T, (02) dP
T(az) r dP.f"op,ar,,.' (3.6)
tnlp:
f'(' I ) dP>&

oRT!' 0
dPP,
fe, (ZI)' (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 quasilinear 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)"
e4ct)  ("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 basistheir 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
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"
a·
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>
/'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.
,,, "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:
T.~.l.l
Compound Z~ CompourKl Z~
Compared to the correlations that we have just discussed. the C':Orftlalions based on the
corresponding slales principle and utilizing lhe linlillie 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,)
Tl (3.16)
I 1
U'I'_
o
DI
Jrl;
_...1 _
,(r '...
('
rial u
....
I
I
I
I
o 'I   1   1 
57
.., ~.S =
~1.'D    .'  
I
I
1.5 +~~"i~""'*""I"I1+.....'liI~~""itIi""""""~=*"'~~rt"
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   ,   . ~~~Tr
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$.
T.b1~ J.]
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
"
75
Z= I +.!!.. + ~ + ~ +
II, 1I, tl,
T;·l (P+ ~)"p(l,)
, II, II, II,
(3.25)
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,
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:
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. 092     ,     ~     
I I " 0,94 0.96 1 0.96 '
• , I I *
, , I I ,
<>.3+jt+I+j
o 0.2 0.4 0.6 0.8 1.2
Redl.lCed pressure
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 lilerconlaining
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 twophase 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
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
~mDouln
It
82
(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,
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)
(3.41)
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].
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$. Those relating
to molecular geometry (bond angles and lengths) are characteristic of atomic groupings..
As for the absorption frequencies. we know that. as a first approlOmatKlIl, they arc related
to the nature of the bond in question and lillIe sensitive to the environment. It is therefore
natural that the thcrmodynamic properties of the ideal gas. molar heat capacity. and the
entropy reported at absolute zero, may be broken down into group contributions.
For molecules or groups. the possible symmetry of certain structures may render several
distinct configurations indistinguishable. For example, such is the case for the three posi
tions of the methyl group due to a 120" rotation around the Ce bond, or even the twelve
positions of the methane molectlle that are also obtained by a lZOO rotation around one of
the four GH bonds. It should clearly be taken iOlO account in the description of a prop.
erty such as entropy that is related to the "degree of order"' of a system. This symmetry is
expressed by the "degree of external symmetry" and the "degree of global symmetry" of
the molecule, The degree of external symmetry f1 is equal 10 the number of indistinguish
able positions that the molecule may aS$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
(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·KI,
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· molI
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, molI. KI 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:
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
CCc.,)(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 ·Kl and ~:94,85caJ·molI·K1
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]
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
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 fiftysiJl methods For the calculation or
critical temperature. fiftyfive for critical pressure. and fiftyrour 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
(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
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.
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.
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.
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 nbutane
We have the melll\ured vapor pressures and "molar densities" of nbutane 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:
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.(IT,""'1 (3.14)
,
in the form:
.".
,
vL"
[(
"_'_,,, T)~
1 __1 
T,
( T)~] InZ
1_...1
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.
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].
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 . molI 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 IOJ
<A600°F)
<,,(IZOO"F) J·rnol'K' 1.421 10< ,.385,
2.4219 1.9136
1.932
3.'
4.2
, I~
"
D
"
I,
U.,
1,
'
c·· C ,5·'0,'
,
, ,
II
95
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tempUalul"e$ of Qrganic compounds. NPL Rep. ell."". 92. National Physical Laboratory.
Teddington. Greal Brilain.
Ambrose 0 (1979) Correlation and prediction of \'apour liquid critical properties. II. Critical pressu
res and volumes of organic compounds. NPL Rep. Cllml .• 98. National Physical Lal)()ratory.
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Ben"", SW. Cruickshank FR. Golden OM. Haugen GR. O'Neal HE. Rodgers AS. Shaw R. Wahh R
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Colllliantinou L. Galli R (1994) A ICI,E. J.. 40. 1697·1710.
Domabki ES. Hearing ED (1988) Estimation of tile thermodynamic properties of hydrocarbons al
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Domalski ES. Hearing ED (1990) Heal carmciliCll and entropia of organic ...""pounds in the
rorKletUed phase. Volume 11. J. /'hyJ.. Ch"",. R"r
Dma. 19.88110048.
Elbro H5. frcdenslund Aa. Rasn'lJ.S5l:n I' (1991) Group rontribution method fO<" the prediclion of
liquid densities as a funetion of temperatu,e fOf SOI~enls. oliBomer! and poIymc:n.lml. Eng. CI.t....
Ra. JO.2S762S82.
Emschwilier G (1959) Chimir /'h)"Jiqut. Presses Univcrsitairc:s de France. Paris.
Gani R. Constaminoll L (1m) Mol..'CUla. structure b;oscd eslimation of properties for process
desiBn . .v.·tnlh Confrrma on fluid proJHrtit~ ,,,,Ii
€Mmklll prlKaS Jaign. Sr>QVo'maos, Co!orndo.
June 1m.
Gubbins KE (1989)Thc fut\l,e of lhennodynamics. Chr.... Eng. Prog.• 8S (2). 3849.
Halm RL Slid LJ (1970) 5.alllralcd IMjuid and vapor densili~ for polar nuids. A IChF. J. 16. 3.
Halm tl al. (19llS) AlOE J.. 31. 1632.
Hougen OA. Walson KM. Ragatz RA (1959) Chc",ir:ul Pro«s~ P"·,,dpIQ. Wiley &.sons..
Johack KG (1984) M.5. lhesis in chemical engineering. MaMaChusselJi Inslitule of Technology.
Cambridge. Mas.s.
Kay WB (1936) Density of hydrocarbon gases and vapors at high temperature and pressures. h,J.
E",.
Ch"m .. 28.10141019.
Keenan JH. KC)"el; FG. Hilil'G. Moore JG (1\169) Sir"", Tt'hlrJ.. Thumodynamk P"'{H"ia "fWa,u
I"duding Vapor. Liq"id "lid Solid Pha<tJ. Wiley. 1\169,
Lu BI. Kesler MG (1975) A generalized lhermodynamic correlation based on lhree·parameler 001·
respondinll stale. A IChE J.. 21. 51().527.
lydel$en Al (1955) Estimalion of rnlital properties of organic compounds. Un;y. Wisconsin Coil.
Eng.. Eng. Sill.. Rrp.. 3.
Meycr EF. RenncrTA. Stce KS (1971) Cohnivc energy in polar organic liquids.ll.llll.· alkyl nilrik'S
and llle 1chloroalkanes..J. PhyJ. Chrm. 75. 642648.
Pittt. KS. Curl Jr RF (1957) Empirical equation for tile second virial coefflCienl. J. Am. ell"",. Soc..
N.2369.
Pitzcr KS.l.ipmann DZ. Curl RF.Jr.. Huggins CM. Petersen DE (1955) Cornpre.,.,;bility faclor. Yllpol
prCMllre and entropy or vaporiz:llion.J. Am. Chern. Soc.. 77.3433.
Radcll HG (1970) Equation of .tate for s.aturat"d liquitb. J. Ch"m. F."!l' Dul... IS, S14·517.
p'
"
Rl>Ck"lI IIG (1971) CakuLatioll of bul>bk point volumes of hydrocarbon miJuures. J. Clrern. Eng.
I)<I'Q. 16. 3O!lJ 10.
Reid Re. Prau,nitz JM. Po1inll BE (1987) TIre f'roputiCJ of Ga>'es "tid Liquids, (ollnh edilion.
McGra ....·Hili Book Co.
Ril'7.i MR. Daubert TE (1980) Simplify property prcdictions.1/fdrocluborr Pux:nsinK. March. liS
116.
Riazi MR. Daubert TE (1987) Charac.erization pam"",!crs for petrokum fflK'lion5. Ind. 1:..,. Chm••
Ro.. 26. 75:5759.
Ria:ti MR Daubert TE (1987) Impl"O\'w cllarlOClcrization of wi<k bniling range unddinW petroleum
fflK'liQlu. lml. En8' Chern. Rt." 26. 629632..
Rial; MR. Oaullcn TE (1980) Simplify property prediction. ffydrtKorlHm PrtX~i"8. March. 1I5
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Riedel L (19S4) Eine neue univendle Dan'pfdrud:formeL CI,m,. £n8. T«h .• 2fdO.
Rihan; ON. Dorai."'amy l.K (1965) Estimation of Ileal capacity of organic compounm (rom group
contributions./&EC flmtlmnrnmh.4. 1721.
Rogalski M, Malo FA. Ncau E (1992) EJtimation of hydrocarbon critkal Prt>Jl'C'rl~ from vapour
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Schmidt G. Wenul H (I'.ll'll) Estimalion of critical data byequation of stale'. Ca"ad.l. ofCMm. E"8.•
59.527.
Silverberg PM. Wenzel A (1116S) 'The variation of latent heat with temperature. J. Chern. £"8' DIlIa.
10. 36.}·366.
Simmnd IHI. Janowsky R. Ohnsorge A (1986) Critical data of pure lub!stancn. Chtmisrry DllIa
$eri~. Volll.l)cc,hcma. F....nkfurt.
Spen.ccrCF. Danner RP (1m) Improved equation for prediction of ""tunned liquid density.J. Chem.
E"8. Dll/II. 17.2.36241.
Spencer CF. Adler sa (1978) A critical review of equations ror predicting satu.... ted liquid density.
1. Che.... £n8' Vmli. 23.82·89.
Stipp GK. aai SO. Stid Ll (1973) Compressibility facto", of polar fluids in the gMI.'OIJ' and liquid
regions. A/ChE I .. 19. 227.
Stipp GK. aai SO. Stid U (1973) Comprn:sibility fllCtor of polar fluid in tl>e ~ous and li!juid
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Thek RE. Stid U (1966) A/ChE I .. 12.599.
l'hck RE, Stid LI (1967) A/ChE J" 13.626.
lhinh TP. Ountn 11.. Ramalho RS (1971) Equatiorl$ impro>e Cp predictions. lIydrocarbon
f'rON's.';",. January, 9S1().I.
T:o<>n","",ulos C (1974) An empirical correlation or seoond yirial coefficients. A fCh E J.. 20, 21iJ...272.
T50nopoulos C (1987) Critical ronstanlsof normal alkanes from methan.c to polyethylene. AfChE I ..
33.2OilO2llO.
Vetere A (1987) Methods for cstimation of critical "olume5 Tht Chemic/<f £Ilsinurins J•. 34, 151153,
Vetere A (1989) Estimation or critical pre5SurC!l hy tl>e Raeken e!juation. Chm,. Eng. Xi.. 44, 791·
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Voulgaris M, Stamataki, S. Mag<>ula. K. Ta$liios 0 (1991) Prediction of physiclll propenieli for non·
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97
This work uncovered a field thaI has been lhe subjt'Cl of numerous studies thaI are still
ongoing. and into which we can provide but a glimpse. In 1983. R.C. Reid presented a sta
tistic on the literalllrc devoted to tile topic and especially all the Redlich·Kwong equation
of slate (Table 4.1). and concluded; "/1 is (I fulllime jQb 1'''$/ 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]
deviations from the ideal gas laws or residual quantities. For cltample. for enthalpy we
have:
If .....e also use the heal capacity in the standard stale. the value of Ihe thermodynamic
properl), may be calculated using:
•
IIa =RTln
(,,_b) •
   (4.5)
, "
yields lhe van der Wilals equlIlion by derivation wilh volume at eonstllnl temperature and
applying &julIlion 1.44:
dA=SdTPdV or da=.fdTPdu (1.44)
,,,
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).
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 liquidvapor 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.
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:
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 equationsthe 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
(ZI)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, (ZI)"
,,
(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
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
8T
dT
lJ..lUt(T.P) = II IJ' = RT ''' (4.14)
"
d8
8T
_ _ ~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
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:
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>
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( ToI"') + [sO{T.P")  soC Tll'P"1I
+ Is'( 7'/')  s"( T.P") I + [sf T,P)  s'( T(tP) I (4.23)
i1(,,')) dP= dB d8
d(ss'h= ( aT /'  dP
dT
and henet: s~=I'
dT
(4.24)
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; dTRln
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 . molI. 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
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:
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:
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:
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 aRTA oTI+TJr 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
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~::!
~ vcb V c
aP) RTc 2.
(3v T=(vcbf+~=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)
ZD 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.
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"Oplll'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 + ",(IV1';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
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 = vb  (C'C:;b",;,~):'(.:,C_'bC,,,,) (4.50)
u~I(T.II) '" !I(T.P.II) 11.( T.P· '" R"T. II ) : [ [T( ~; tp] dll (2.28)
( d'lI"
II(T.II),j·(T.II): aT dT ~
d,
(lIb'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
~
~
~
"'"
".
Fugacity Coefficient
First we will calculate the residual Helmlloltz energy for a given lemperalure and volume:
I.e.: .
a(T.v)  a (T.v) "" f' (
..
 RT
 + RT +
vb v
•
(vb'J(v brJ
) d. (4.54)
a(T.v)Q"(T.v} I (vb) • ( ,)
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(vb) •
RT = In RT + Z I + bRT U(v.b.r,.rJ (4.56)
1 quati
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~
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
+pVp"'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. mol1 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(lIb) • b
InqJ=ln +ZI (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 PengRobinson 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.
'" ,
,, 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·RedlichKwong (   ) and the Peng·Robinson ( )
equalion~ of Slal~. Comparison 10 experimenlal dala ( l>.).
" j
4. f"u•• rionsol5Mc 125
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 SoaveRedlkh·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.
(4.37)
4. Equar......,ciStotre 127
RT,
e:=£2"  (4.73)
P,
n.. i~ the smal1e~t positive root of the equation:
(4.74)
(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.J0982Ctl0.2959J7ro1 (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.
5 ,,,,
.'
, , ,
o '00
"" 300 <00
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:
RedlichKwong Equation: y= 1 and c '" 0
(4.82)
2
PengRobinson 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. RedlichKwong. and PengRobin!;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. Thererorethe 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 · molI. We furthermore
ca1culated the value thai corresponds to the van der Waals volume (135.4 cm J • molI)
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 . molI.
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)
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
vb
•
lI(v+b)
b (b)']
[ lr+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 PengRobinson 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 nonpolar 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.
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)
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 30.2910
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
(IMtlsde<;aline)
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,
[ (XGY)
] m [C,y] (4.88)
I (.tezy)
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
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
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
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 PengRobinson 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'(aI)[J'1+Ja'1(aI)'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'·mol1j "
Methane 151.19 20m 0
Elhan<: 226.48 JO" '.899
Propane
,,·auI.ne
26353
293.52
41.37
52.11 •.'"
3,206
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 "quasiexperimental" 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 vaporliquid 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:
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. nbulane. 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)
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). ror
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 lionana·
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.
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:
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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Ely JF (1985) An C(jualion of Slale model for pure COl and COl rich mixtures. Gu.r /'roca.urs
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Ie I"mre d" "p"l.ion dt '''''' ,ItT Woo'" Bdilion~ Tedmip. Pari$.
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I
5 Characterization of Mixtures
(5.1 )
144
x = Ni (S.2)
, N,
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)
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
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 )
I .. !!!
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'''''''
 ';
~
~
,
.,
,."
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 gasIn 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..
5.2.1 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",VdPSdT+ L, IljdNI
or. by applying the GibbsHelmholtz equation:
G V H
dRT"'RTdPRT2dT+~ (5.14)
150 5. CfwroKrerizdtion oi Mi./lJff:S
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:
Gibbs energy. an extensive variable. is expressed from Ihe contributions of each phase:
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:
p'
I
S. ChdrilClenZdrion 01 Mb,rUffS 151
It is called the generalized GibbsHelmholt: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: sec:alled GIbb5Dubc: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 GibbsDuhem equation allows us to apply a test of coherence to them. In certain
cases, the equation also allows to complement incomplete data.
(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.
Pi:O (:~I )r.P.N; ; (:~i )1~SNI '" (:~ tN,= (:~I tV.N1 (5.2])
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. we note thai the equality of chemical potentials at equilibrium between phases
resul15 in that of fugacities:
(5.30)
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 ) hjh;

( 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:
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
(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 Il/:
(5.36)
and we use the expression 5.17 to write this equation in the form:
1'he difference between the chemical potentials in the mixture and In the reference
stale may bc expressed in terms of fugacity. We have:
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
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 GibbsDuhcm equation:
, . =0
LXi(d In Uih,. (5.44)
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.
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)
(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.
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)
PYI
[, f'("i 
RTin  '"
0
RT) dP
P
(5..54)
lbe ratio: /;
4'i '" PYj (5.55)
o EXAMPLE 5.2
Methane propane mixlure: calculation of fugacity in a mixture
I II =
RT
p + B(T.y) (5.10)
i . 
,
i
p
.]
J
1. I
. t.
~.
. 1 '
0 o.
o. 7
au
159
5.7.1 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)
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)
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)
"",r,dp,
, , ",0 at constant temperature and pressure (5.71)
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).
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
~.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]
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)
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:
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)
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
By applying Equation 5.75. we would have derived the expressions for actiVity coeffi
cients:
(2B U  B l.lB U )P 1]
Yt=exp [ RT .f 2 • (5.8.5)
T."s.s
E>:pl'C$5io<u for fugacity in miJuure~
We nOle thai the 5eCOIId method is never applied 10 the vapor phase. The approaches
....ill therefore be characterized by the calculation method applied 10 the liquid phase. or
course, what we aTe Slating here for the calculation of fugacity is equally valid for the other
thermodynamic properties..
Throughout the previous discussion. the mUlure properties were related to whal is
conventionally called symmetric reference stales. In IheK reference Slale$, 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)
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: liquidVapor Equilibria
p'
168 ~. MixIure.;; liquidV"IXIt" Eqviljbri~
Tab... 6.1
Liquidvapor 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 LiquidVapor 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
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 npenlane. 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$:
N1",NLx/+NvYi (6.1)
For example. a\ 4WC,x 1 '" O.34.y\ '" O.B3, and the vaporized fraction is equallo;
In general. vaporization of 11 mixture progresses up to the ~dew point", The mixture still
verifies the liquidvapor equilibrium conditions, but the liquid phase disappears. The coor·
dinates of this point are the dew temperature, the composition xi...... of the liquid phase.
and Y,,<l<.. " z; of the vapor phase. In the case of the equimolar mixture of propane. with
npenlanc at a pressure of S bar. the dew lcmperalun: is 67.5"C and we have XI = 0.13.
If ""C continue to apply heal 10 the system. it b«omes homogeneous and we s.ay thai we
are dealing with a "superheated" vapor.
The description of the vaporization processes may be repeated for any composition of
this binary miKlure, The bubble points describe the "bubble curve" and lhe dew points the
"dew curve~. Tht.'SC two curves lhat dclimitthe twophase range meet on lhe axes repre
senting the pure substances as lhe bubble lind dew temperatures coincide (monovariant
system). Under lhe bubble curve is the range of the homogeneous liquid phase. lermed
"subeoolcd", and above the dew curve lhe zone of the "superheated" vapor phase. Inside
the lens.. the S)'$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 lwophase 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.
The graph of the isothermal liquidvapor 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 npentane 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 npentane.
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 phasesliquid and vapor. finally the disappearance of the last bubble of
vapor at "= 5 bar (bubble pressure). and the compression of a homogeneOU$liquid phase.
172 6. Mixru.....: U"uidII"1JOf fqui/jbri~
",,
,
• '
,,
, • ,
• ,,
, +rt,1
, ,., 0.75
'"
t1prt 6.) lsollJ.crmalliquid·vapor equilibrium diagram (T .. 300 K) for
the propane (I) ,,·pentane (2) J)'$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 SoaveRedlichKwong 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 _.!"""
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 twophase mixture. Yel. we will n~ observe a bubble
point. and wilen the CTitical pressure (108 bar) i$ rca.:hed. the liquidYapor 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
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 twophase region inside which this
mi;fture splits into two phases. lind outside which it is homogeneous.
In this same diagram, we have drawn the twophase 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'"
.... ..•...
...................... ~~ ..
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 locusthe 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"'Ophase 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 liquidliquid equilibria.
the twophase 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.
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
liquidvapor 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
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
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,
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:
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
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 liquidvapor 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
n,,,___
Pi' "p [(vtIl;)(PPf)] (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:
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 liquidvapor 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 /Ipentane 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
molI)
.,
(C111 J '0101 1) < ,
,OJ
"""'~ '"0.725 OJ In
,,·Pentane 1203
"' 0.256
'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 liquidvapor 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.
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.
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
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:
[( '.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;quklV.lpOf EquiUbri~ '.5
In this equation. we note that:
YI (a.r)
'l,,,
Un 1;1'
+Y2
(a.i)
~y
U I
0
U'
We therefore obtain:
(6.13)
(:) ",,"
1 1;1'
j,l1=S+X,(:) ,,"
1 T.r
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 GibbsKonovalow 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:
• •
L , L Yl ,
• p' ,. ,Yi II,
,. , h,
or:
,.L, y,d _ ' =
RT RT
dP
RT2
dT
therefore. we have:
AVdPASdT=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.
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 GibbsDuhem 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 GibbsDuhem Equation (5.18) and the bond
between the mole fractions of a binary mixture:
x,+.r~=1
then:
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 RedlichKister equation (see Chapter 7. Section 72).
If the data are not isothermal. the generalized OibbsDuhem 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>sDuhem equation be
applied to the calculAtion of the bubble pressures by Slepwise gnphical integration. The
..8 1>. Mixw..,.: LlquidV.opor fquilibtj~
resulls are oonlpllred 10 the experimental values. This method is applied with greal
diHicully and is hardly ever used.
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:
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 .. GLN,~, (5.36)
189
0... ,          ,
<> ..
, <>'"
•
'\;.
<>'"
}. 8
, ,
<>.'" , ,
, , M
~..AN
M',
<>, p /
o"
0.12
0
•
0.'
•
O. •
O.
•
0.' ,
UoIIl rraction at hexatWI
(5.63)
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 )
I I, I'
 i' ;= I." (6.2)
or equilibrium coefficients:
,
K; = ....!. (6.3)
';
or again II equations. Finally the equations for mole fractions:
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.
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 twophase 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.
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,
We will not go into a detailed description of the algorithms that have been proposed to
solve the liquidvapor equilibrium problems. However. some examples will allow u.s to
sptcify the principal dirfK1llties.
193
are combined to give us Ille equation know" as the bubble point relationship:
L, K;.r;= I (6.20)
(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'
(6,22)
are combined to give us the equation known as the dew point relationship:
(6.23)
whieh must be validated.
195
'(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.
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&
By dividing the numerator and the denominator of this equation by }:N1and using tile
vaporized fraction defined as:
N"
F"NL+N
;;". .,iI
(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
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.
""","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
"""'"~
..Pentane
..,
K
0.736
,;K
0.0593
0.6793
K
.,OJ
O.SS4
,;K
0.0798
0.903
K
6.\56
,;K
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:
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:
'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). /Ibutane (40% moIR.). isobulane (40% molar).
npcnllmc (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 twophase
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 . molI, 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$, and the constraint equations yield 2n + 2 equations for the 2n + 4
variables. According to the type of problem. twO of the equatiom such as T  r "" o.
r r "" O. NY _ NY. "" 0, vv· .. 11. H _ H· = O. etc.. complete Ihe s~tem. This is not linear
as the products of the number of moles times the compositions ligure into the material bal
ances. and as the e'luilibrium equations most often involve the mixture fugacity coeffi,
cients or the activity coefficients. and the expres.~ion for thcse quantities as a function of
temperature, pressure. and composition. mllY be complex. The same is true for the volume
or enthalpy expression. We Iherefore apply the NeWlon method for the resolution of this
2n + 4 s~tem. which requires prior determination of the expressions for the Jacobian vari,
abIes of this system. namely the derivatives of eaeh one of Ihe equations that we want 10
solve ,.ilh respect to thc variables (T. P, NY. NI., XI' YI)' expressions thaI are dependent on
the models applied to the mixture (aClivity coefrlcients. equations of state. etc.). We note,
however, that from one problem to the next. only the last two equations vary. Their nature
is related to the type of problem we want. such that the method has a degree of apprecia
ble generality. It was introdl/oCed by Asselineau .,1 at. 119791. After resolving the problem. a
simple extension allows for the determination of the derivatives of the equilibrium condi
tions relative to anyone of the variables. Of course. this kind of system may be simplified
in specific cases of bubble point. dew point. or partial vaporization at given temperature
and pressure.
A second set of methods is based on the minimization of the Gibb$ 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).
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)
(6.4)
(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. 6915.
A_linea.. 1., Bog<lanic G. Vidal J (1979) A venat;'" algorithm for calculating ,apourliquid cquili
bria. 1'7,,/<1 Phtu, Equilibri... 3. 213290.
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. 145160.
Gmehling J. Onken U (1978) Vaporliquid equilibrium data colleclion. Chemi,try Da/ll Serin.
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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.
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Michelsen ML ( 1985) Simplified nash ealculations for cubic c:quation. "f stale. 111I1. ""g. ehe",. 1'",,,.
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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 liquidvapor 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 liquidvapor 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.
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 ethanoillheplane 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 ndecane mixture shows that it may. however. reach 4 J . Kl . molI. 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",
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
".,
,
~ " .•
~
"..
" "., "' J0
".,
1.0
V
0' "
""'1"1' 703 Exccc$5 molar heal capacities for the 14dioxan (1)
cydobcXIlllC (2) $Y!'!cm jTrejo <:1 al.. l\1911.
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;
"""
900 8.
,.
(J·moI')
"
60 b.
'"
tIflU~
1.5 Variation of cxcc:ss enthalpy of Ihe nhexane nhcxadccanc
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 abovementioned 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.
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 liquidvapor 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
figure 7.6 Variation of llle excess enthalpy for too etballQI (I)
....ater (2) S)'Slem with temperJI[urc {Larkin t/ al.• 19751.
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
" "
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
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$ure (61'). Calculating the pressure fOf" the values of the com
position and temperalUre taken as ~lrue", we may relate the relative uncertainties at these
quantities to the pressure by defining a "resulting uncertainty" t!J".
where (75)
where "c.p and "par respectively denote the number of experimental points (except tile
pure substances) and the number of parametcl'lI (equal to one in the previous example).
This average quadratic deviation 0,..
according to it$ 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·
mVlItiOIl 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
melhanoillpropanol 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
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.
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
nonlIeJIiJibIe 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:
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
~,
""'
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
(5.75)
we get the following expression for the activity coefficients (which are always less thlln I):
(7.10)
(7.11)
1 1
In ri",ln  + 1 Inr;lnp+lp
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 IOJ
10 0.245
100 2.7 101 1O~
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 nparaJftns.
[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:
....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:
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
steond. 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'
• •
,
,, •
,
,, • '"
,
,
•. ~. • '..... ~
, ....
••• "
•,, , •••
," , '., ~
•
such Ihat for one mole of mixture. the expression for the exeess internal energy. or 10lernal
energy of mixing. bewmes:
Note that only the differences belween Ihe molecular interactions, ~I  f: 1.1· £l.l  eu
appear in this expression.
p'
229
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:
"
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.Ie,.ItuJxIX~=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).
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
/11.1"U
The equilibrium constant K is related 10 the energies of interaction G.; by the equation:
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).
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(£lllU)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:
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:
'"
that is not fulfilled by the preceding definition equation for these parameters. On the Olher
hand, the quasiehemkal 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.
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 [MoelwynHug.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;
.=('II·'I?)~
, v;.r (7.16)
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)
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 liquidvapor 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
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 nheptane
(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 liquidliquid solubility. solid.liquid solubility. as
well as ill gasliquid 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 liquidvapor 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 /ltelradccane system clearl)'
GI gE T_283.15
• gE T.293.15
• gE T.303.15
• gE T306.15
• 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
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 ScalchardHildebrand 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 IIheanc (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.
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 liquidvapor 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 liquidvapor equilibria.
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:
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 liquidvapor 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.
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 nonrandomness parameter", which is ill fact empirical. ill
introduced to yield:
xc~p(_a._Cj,l)
I IJ RT
[\ 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
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 GibbsHelmholtl: equation, .....e obtain the ellpression for ellcess entbalpy
(heat of mixing), and the simultaneous correlation of liquidvapor 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 liquidvapor 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 nonideal 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
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
liquidvapor 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 nonpolar 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 liquidvapor 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 liqUidvapor and the liqUidliqUid 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 ofcontaining" 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.
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
..
2",9~ ft./
where:
In opposition to the approach used for the NRTL model. and this is essential. we apply
the GibbsHelmholtz 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 St8VennannGuggenheim (Eq. 7.13):
(7.13)
(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 GibbsHelmholtz equation is
generally possible only if we take into account parameter variation with temperature.
which doubles their number.
As for liquidliquid 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 liquiclli.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)
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)
(7.44)
where m.,1 and ".,1 were obtained by liquidvapor equilibrium data regression.
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 StavermannGuggenheim exprCSliion:
(7.13)
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:
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
~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:
IIn (8I l1'L1 + l3:!¥'l.l + 8)".).1)
8 1 ¥,u
which is:
1 In (0.4965·] + 0.ISSI1 + 0.345 40.927)
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 + 0.15810.2595 + 0.345 4·]
and therefor.::
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:
~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
Wilh alcohol hydrocarbon mixturn one of the components in the pure state is "poly·
merized" by autoassociation. 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.
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
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 liquidvapor 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 liquidvapor 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 liquidvapor equilibria of electrolyte solutions. It uses an
Since the model was developed from liquidvapor 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
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. IIpropanol. acetone. and nbutanol. 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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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
liquidvapor 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.
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 SoaveRedlichKwong. of Peng
Robinson. of SimonetBeharRauzy. 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 SoaveRedlich·Kwong that we introduced in Chapter 4 tlsing:
NT .(T)
p=    (4.42)
vb 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)
(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)
TabkLI
Psclidocrilitl!1 points of tilt: equimolar mixtures methane n~.ne.
and ethane ben7.ene
~
Methane, IIoc: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$OfI cl ..I.
504.74
425.02
362."
410.23
3.73
338
3.06
3.45
469SS
..D(
426.99
","
.,."
..,
'.Ol
l1:ja
Pe<kncn ~ ../.
41023
429.48
3.45
3.50
","
443.4
,."
'.Ol
274
",,
,.. ,,
,,
, ,,
,
,,
,,
•., ••
•
••
•
••
•
••
•
•
•
••
3.'
••
••
•
'i~ ..
~. "
3
.
..........., ",.
'~ '
Of course. it is important not to confuse the pseudocritical coordirmles. which are the
parameters for a modd only, with the ··truc~ critical coordinates. The true critical point
(Chapler 6. Section 6.1.2) relates 10 conditions of temperalure and pressure that charac
terize a real. experimentally observable physical phenomenon in which the two phases in
liquidvapor equilibrium become indistinguishable. They may differ considerably from the
pseudocriticaJ coordinates. For example. in the elhane benzene mixture. the critical pres
sure reaches 10.5 MPa while the pseudocritical pressure docs not go above 5.35 MPa. For
hydrocarbon mixtures with very different molecular weights. critical pressure may reach
several hundred bar.
277
N ( Olnrp... ) ar,
:=.;;;;:;rT T 1 ohh' (T )hh
0l(To 1
I) (8.19)
, aT, T.f!'vi aN! RT '... ' T<.<fl RT,... T, T<JII
A series of analogous calculations yields:
N "",) ai',
=(21 )( 
i'o I ) (8.20)
(
, ap, r:1'.N! aNi P,,,,,
Finally. applying II linear mixing rule [0 the acentric factor gives us:
And ultimately:
hh' (T
1 u 1 ) (ZI)   1
In19;=lntp... +   
RT,,,,, T, T,.""
(P,,)
P"",
If we apply the Lee and Kesler method thaI uses the simple fluid properties (w=O) and
the properties for a reference fluid with acentric factor r.J'I. for any residual term. lind
especially for the fugacily coefficient of the mixture. we slate:
(In rp)("_ (1n rp)IO)
'" .. 0 <', ,)(0).;. w... w(,l
At this point. we shall return only very brieny to thl$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~
(5.11)
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 liquidvapor 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)
in which the values for parameters '1 and '1 are characteristic of the equation in question.
as secn in Table 4.6.
In general. we l:ombine thcse equations of state wittlthe socalled "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 (ScalchardHiJdebrand
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!\.
,
C = LCil i (K.30)
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:
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:
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 PengRobinson 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 nonpolar 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
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 SoaveRedlichKwong method could be applied 10 mixtures of
chlorofluorocompounds. 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 liquidvapor 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 SoaveRedlichKwong
or PengRobinson 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..
"
•
• •
.
,..
•

...~ f""'
, r("
o " ,co
Temoerature I"CI
Figu~ lU Critical points loci for carbon dioxide. pal1lffinl C 1C ,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
,
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.
In theory, the interaction parameter kij within the calculation for the binary term IIL/
1Ii,j=v'II;./liJ(lkij) (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]
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 "lightheavy"
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
(lkd b
z
and it is understood that the values for Pf and "2" validate the equation of statc and
the liquidvapor 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
(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
,
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 liquidvapor 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.
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
SoaveRedlichKwong 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:
for the pure substances as well as for lhe mixlure. Therefore, we may state:
it being understood that these fugacity coefficients are calculated using Ihe equation:
P(IIb) •
lnfl:In RT +21+ bRTU(v,IVI.r1J (4.57)
If we use the Soave·RcdlichKwong 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..)
o EXAMPLE 8.3
Characterizing the roots of the SoaveRedlichKwong 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
'5f,.~~~.,....~~~~~~......~~~~~~..~~~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 liquidvapor equilibrium at 4O"C at a pressure of
2S bar using the equations:
ro' ro,
I YI'" I '.T 1
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 welldefined 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)
(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:
~"
;
';
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(Ik lJ )
(b , i bJ)
2
300
, P(MPa)
,
P(MPa)
'.5
,,,
,
,
, 5
'5 •
'.50 r, '.50 10',1,
'" 0.75 10', 0.75
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 liquidvapor 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"luidvapor e"luilibria or the acelon~ ""'thanol water 5)'5lem.
Average quadratic devialions for the calculation of bubble temperatures.
EJcperimenral data [Griswold. 1949. 19S2]
328.333 0.45
I.,
323343
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 RedlichKisler 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 PengRobinson 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
In light of the remarkable results thai they provide. and also because their expre$ion can
be regarded as complex. we shall develop the5C' methods proposed by Pl!neloull t'I Ill.
I I989J in detail.
The equations of state that we are considering are fOllnd in an especially simple form as
a function of this variable. So. if .....e state:
(8.47)
This observation may be generalized 10 all the equations of stale derived from the VBn
dec Waals theory. which can be wnnen in the form:
1
Z.    01/11'<11) (8.49)
1 ,
For the van dec Waals. SoaveRedlichKwong. and PengRobinson equations. (l is inde
pendent of packing fraction. and depends only on temperature and. for a mhuure. oompo
silion. The \I" function itself depends only on the packing fraction and lhe chosen equation
of stale (via ttle intermediary of constants '1_ '2)'
b Nb dV dll
11""'
, V "d V
.  ,
at COIlstanl numbcr of moles. such that:
dA T ", ,
NZRT
dry
For the ideal gas (denoted by superscript I). the compressibility factor is equal to I. and:
• NRT
dAr'"   d ,,
The variation of residual Helmholtz energy with packing fraetion is therefore equal to:
d(AA')," NRT(ZI)dry
,
If II ..... O. then AA' ..... O. and we derive:
AA':NRT
f,
~(Z1)
, dll
8. IIppIkarion 01 fqwriom 01 Sf,,,,, 10 Mixtures 305
The first term corresponds to the miJuure in the ideal gas state. However. neither the
pressure nor the molar volume arc constant:
b
."
v '" bj v'" 
"
In order to calculate this term, we use a reference stale defined by the value for molar
volume. "0. at the same lemperature. of OOUI1iC. [f ar
stands for the Helmholtz energy of
the comp<ments, and aO for that of the mixture. both in the ideal gas state. in this reference
state:
v b_
a r(T,I1) '" aj RTln ' '" oi RTln  ' 
VO 11 .,°
and: a'('{,I1) '" 0° RTln " = 0°  RTln
b
VO .,° 11
therefore:
0"
Furthermore, we know that for an ideal mixture of ideal ga$C$ aehieved at constant vol
ume (or prcssure):
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:
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
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:
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)
p'
307
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).
(8.61)
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 liquidvapor 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:
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.
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 chloronuorohydrocarboll$.
It is known IAssclincau er al., 19781 that the Soave method combined with the classical mix
ing rule allows us to calculate lhe liquidvapor 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 liquidvapor 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 liquidliquid equilibria pre
313
, T.523K
• • • • • EXPER
MHV'
~
~ • r. 473 K
J •
, T. 423 K
0+,1
o ,
flIu~ III I Pfldietion of liquidvapor 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.
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$Jlu"" Like the MHV2 method. it may use Ihe models
(eJlpressions and parameter values) that already exist. In addition. it retains the quadmtic
variation of the serond vinal coefficient, This method is based primarily on the expression
for excess Helmholtz energy at given pressure and temperature.
The residual Helmholtz energy is expressed by til... equation:
P(IIbj .. .,+b
au'=RTln  In (8.78)
RT h "
314
Applying this expression to the mixture and its components 8t the same pressure and tem
perature. we derive from it theexcus Helmholtz energy althe given pfC$ure and temperature:
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)
B= L, 2A,ft
I
rtj (5.11)
8 ..1+ 81J
where: BiJ= 2 (IIv) (8.84)
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 liquidvapor equilibria using the Woog
and Sandlcr m<:lhod [Hernandez GardlJZll. 1993]
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.
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 nonpolar 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 IhreepllaR 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 threephase 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 antihydrate additive. The problem is fUrlher complicated by the presence of water.
Liquidvapor 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:
The mixing laws aTt then applied [0 the liquid phase of composition xi_ for example:
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)
(8.33)
p'
8. loppIic~/ion of [qwriom 01 Sidle !O Mix/Ufe! 319
In fact. the calculation of liquidvapor 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 ~liquidliquid" equilibria and "liquidvapor" 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 twophase 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 liquidvapor 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.
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
twophase 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 (nonlinear) 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
capacitiesCIC.. 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 liquidliquid 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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