Fluid Phase Equilibria, 95 (1994) 109-121 109

Elsevier Science B.V.

A partial molar fugacity coefficient useful for changing

mixing rules of cubic equations of state

Akanni S. Law al * and Ernst T. van der Laan

BP Exploration (Alaska) Inc. P.O. Box 230336, Anchorage, AK 99523 (USA)
(Received July 21, 1992; accepted in final form September 25, 1993)

ABSTRACT

Lawal, A.S. and van der Laan, E.T., 1994. A partical molar fugacity coefficient useful for
changing mixing rules of cubic equation of state. Fluid Phase Equilibria, 95: 109-121.

A cubic equation of state (EOS) is used to develop a cohesive technique for the partial
molar fugacity coefficient of a component in a mixture. The technique simplifies the
determination of fugacity coefficients for any type of mixing rules by the introduction of a
differential operator and logarithmic transformation of a mixture property. The technique is
very attractive in that it introduces functional modifications into previously established
mixing rules of pressure-explicit equations of state, and offers a unique opportunity for a
unified fugacity routine in PUT packages and process simulation models. The technique
accommodates density-dependent mixing rules as well as non-cubic equations; any type of
mixing rule with varying levels of difficulty is admissible by the differential operator, without
starting the derivation of mixing fugacity coefficient afresh. Several mixture rules are
presented to show the judicous use of the differential operator for the partial fugacity
coefficient.

Keywords: theory, equations of state, cubic, mixing rules, fugacity coefficient, partial molar
property, phase equilibria.

INTRODUCTION

First introduced over ninety years ago as a substitute for the chemical
potential, the Lewis ( 1901) concept of fugacity is used more than ever
before in the formulation and solution of problems in phase and chemical-
reaction equilibria. In such problems, the calculation of fugacities from PvT
data necessarily involves differentiation with respect to the mole fraction
and an algebraic representation by means of an equation of state appears to

* Corresponding author.

037%3812/94/$07.00 0 1994 - Elsevier Science B.V. All rights reserved

SSDZ 0378-3812(93)02440-X
110 A.S. Lawal and E.T. van der Luan [Fluid Phase Equilibria 95 (1994) 109-121

be desirable. However, in phase equilibria calculations, it is often the

composition of an equilibrium phase that is sought; this obviously requires
knowledge of the functional dependence of the component fugacities A on
the composition of the phase. Although any such detailed knowledge must
ultimatley come from experiment, thermodynamics does impose constraints
on the nature of the composition dependence. Our purpose here is to
develop these constraints, and to present quantitative features of the com-
position dependence of J; that would be useful for the van der Waals
family of equations, and greatly facilitate the treatment of various mixture
rules in cubic equations of state.
The development of the composition dependence off; for multiparame-
ter equations of state is a difficult and challenging problem when the
prescribed mixing rules (Mansoori, 1986) of the equations of state are
changed from those established by the original investigators. ln the case of
multiparameter cubic equations of state (three and four parameters), it is
not a trivial task to derive and implement the mixture fugacity coefficient
(Smith and Van Ness, 1975; Van Ness and Abbott, 1982; Model1 and
Reid, 1983; Walas, 1985). There are many established cubic equations of
state (see Table 1) whose utility has not been extensively tested because of
the lack of a cohesive technique of generalizing the composition depen-
dence of the component fugacities for the various types of cubic equa-
tions of state. Attempts to find a common basis have been restricted
to two-parameter equations of state (Huron and Vidal, 1979; Prausnitz et
al., 1986; Szarawara and Gawdzik, 1989; de Leeuw et al., 1992) and a
three-parameter equation of state (Olivera-Fuentes, 1991). Unlike the ap-
proaches of Topliss ( 1985), Szarawara and Gawdzik ( 1989) and Olivera-
Fuentes ( 1991), a differential operator is developed for all types of mixing
rules for which the partial fugacity coefficient is the starting point. The
differential operator established in the paper is useful for deriving the
partial derivatives of other thermodynamic properties (Michelsen and
Mollerup, 1986) and for simplifying the derivation of the Gibbs partial
derivatives that have recently been reported by Abbott and Van Ness
( 1992) and Mollerup and Michelsen ( 1992).

CLASSICAL EQUATION OF STATE

Let us consider a four-parameter modification of the Lawal-Lake-

Silberberg (LLS) cubic equation of state, illustrated in this paper by
(Lawal et al., 1985; Lawal, 1987):

a(T)
v2+abv -Bb2 (1)
A.S. Lawal and E.T. van der Laan / Fluid Phase Equilibria 95 (1994) 109-121 111

TABLE 1
Common specializations of the LLS equation of state

Coefficients of the quadratic

Authors Year u P a-B

Two-constant equations:
Van der Waals 1873 0 0
Dieterici 1898 0 0
Berthelot 1990 0 0
Redlich-Kwong 1949 1 1
Peng- Robinson 1976 2 1
Harmens 1977 3 1
Zakharov 1977 C l(c = b)

Three-constant equations
Clausius 1881 2clb c2/b2 l(c = b)
Martins 1979 2 t2/b2 l(t = b)
Schmidt- Wenzel 1980 1+3w 30 1
Harmens-Knapp 1980 (c - 11 1
Heyen 1981 yb + e)/b elb 1
Joffe-Martins 1981 2c/b c2/b2 l(c = b)
Patel-Teja 1982 (b + c)lb c/b 1
Kubic-Martins 1982 2clb c2/b2 l(c = b)
Yu-Lu 1987 3+w w 3
Yu-Lu-Iwai 1987 (3b + c)/b c/b 3
GuooDu 1989 2clb clb l(c = b)

Four-constant equations:
Himpan-Danes-Gaena 1979 2d/b (d2 + c)/b2 l(c = 0, d = b)
Lawal-Lake-Silberberg 1983 B E-B
Adachi- Lu 1983 b, + b,)/b bzW2 l(b,=b,=b)
Trebble-Bishnoi 1987 (b + c)lb (bc - d2)/b2 l(c = b, d = 0)

It is more convenient when presenting residual properties (enthalpy, en-

tropy, fugacity and fugacity coefficient) to represent eqn. (1) as
1 A
I=--
Z-B Z2+2yBZ-j3B2
(2)
where

y =a/2 A = a( T)P/R2T2 B = bP/RT Z = PvIRT (3)

By assigning certain integral values to the arbitrary parameters a and fi,
eqn. ( 1) and (2) take the same form as the familar cubic EOS. Examples of
these are the van der Waals ( 1873), VDWEOS (a = 0, p = 0, a = a(T)),
112 AS. Lawal and E.T. van der Laan / Fluid Phase Equilibria 95 (1994) 109-121

Redlich-Kwong (1949) RKEOS (a = 1, /I = 0), Peng-Robinson (1976),

PREOS (c( = 2, fi = l), Harmens ( 1977) (LX= 3, fi = 2), and Schmidt-Wenzel
( 1980) SWEOS (a = 1 + 30, /3 = 30). Other examples of cubic equations that
have been transformed into the form of the LLSEOS are shown in Table 1.
Equations ( 1) and (2) offer the distinct advantage of providing equations
of state of the form described by Walas (1985) as variants of the Redlich-
Kwong equation (1949), because the sum of the arbitrary parameters
a + /? = 1 or a specific constant. The form of eqn. (2) provides three desirable
advantages that are not immediately obvious: (a) the discriminant of eqn. (2)
designed as D = (y2 + p)“.’ is always greater than zero, since j3 3 0; (b) the
introduction of y into eqn. (2) makes the factorization of the quadratic
expression more convenient, guaranteeing the presence of a single horizontal
asymptote on the critical isotherm in the P-v plane of the EOS (Abbott,
1989). Thus the two simplifying procedures are essential in eqn. (2) for the
development of the partial fugacity coefficient without the difficulties recently
reported by Olivera-Fuentes (1991) and de Leeuw et al. (1992). The third
advantage will be discussed later in connection with the separability of the
four parameters in eqns. ( 1) and (2).

MIXTURE FUGACITY COEFFICIENT

The fugacity coefficient for a single component may be expressed in terms

of the compressibility factor using the thermodynamic relationship (Smith and
Van Ness, 1975)

In+ -ln(J;/P) =
p(Z- I)? (4)
s0
Equation (4) can be conveniently applied to any pressure-explicit equations
of state. By substituting eqn. (2) into eqn. (4) and performing integration by
parts (using the tables of integrals from the Handbook of Physics and
Chemistry, Beyer, 1980), the working form of the fugacity coefficient for a
single component is established:
In4 =ln(J;/P) =(Z-1)-ln(Z-B)-Q (5)
where

A/Z ify=fi=O (VDWEOS)

(
A Z+B
B In z if y = l/2, j3 = 0 (RKEOS)

Q= A Z+yB+DB
ify#O,P#O (LLSEOS)
l- 2DBlnZ+7jB-DB
AS. Lawal and E.T. van der Laan / Fluid Phase Equilibria 95 (1994) 109-121 113

Equation (5) can be solved using the values of a and /3 that are listed in
Table 1. The fugacity coefficient, 4, in eqn. (4) can be used to define the
fugacity coefficient 4z of a component i in a mixture:

41=f;lx*P (6)
whereJ; denotes the fugacity of the component i. By analogy with eqn. (4),
& can be expressed in terms of the partial molar compressibility factor using
the following thermodynamic relationship:

In 4, = p (.Zi - 1) $ (7)
s0
where

(8)
or

Equation (8) is derived from the usual definition of partial molar quantities
by replacing mole numbers by mole fractions (Van Ness and Abbott, 1982;
Walas, 1985) and the partial differential operator, A,, which is usually
obscured in textbook derivations of partial molar quantities is thereby
identified:

(9)

The derivation of the component fugacity coefficient & in a mixture from

eqns. (7) and (8) can be simplified. In the case of a single component, it is
always advantageous to manipulate the variables somewhat before applying
the equation of state (Lawal et al., 1985). For mixtures it is much more
convenient to adopt a calculation in which the order of differentiation with
respect to the mole fraction (eqn. (8)) and integration with respect to the
pressure (eqn. (7)) is reversed. One way of accomplishing this task is to
define the molar quantity U by

(10)

By substituting eqn. (7) into eqn. ( 10) and changing the order of integration
and summation, we arrived as expected at

u=
sp(z-l)$
0
(11)
114 A.S. Lawal and E.T. van der Laan 1 Fluid Phase Equilibria 95 (1994) 109-121

Expressing eqn. (7) in terms of U is accomplished by substituting eqn. (8)

into eqn. (7), changing the order of integration and differentiation, and
using eqn. (11) to introduce U and aU/ax, into the intermediate expres-
sions; the procedure simplifies to

(12)
Equation (12) can be applied to any equation of state using expressions
for U and au/ax,. The calculation is lengthy, but made clearer via the
introduction of Ai.

PARTIAL FUGACITY COEFFICIENT

For reasons that will become apparent in later examples of the applica-
tion of the Ai, it is more convenient to consider U of eqn. (2) (by inspection
of eqn. (5)) as function of In 2, In A, In B, In yrn and In Pm. Applying the
chain rule and realizing that A, is a differential operator leads to the
following expression:
In 4i E In (J;/x,P) = U + Z( aU/&Z) Ailn 2 + A(ClU/aA) A, In A
+ B( 8 U/aB) A, In B + Y,,,(a U/ay,,-,) Ai In yrn
+P,&WW,) AJn Pm (13)
The third advantage of simplifying the quadratic expression of eqn. (2) is
obvious from eqn. (13): the mixing rules of parameters a,, b,, ym and Pm
have been separated through Ai. Equation ( 13) provides a more convenient
starting point for any level of mixing rules. Evaluation of Z(i3U/aZ),
A(a U/CIA), B(i3U/aB), ym( aU/8ym) and j?,(i3U/i3/?,) has been carried out
elsewhere; the detailed calculations can be obtained from the authors.
Equation ( 13) yields the following expression for the fugacity coefficient &
of a component in a mixture:
ln +I = In (J;/x,P) = (Z - 1) - In (Z -B) - Q - QAi In A
+(Q+Z-l)AilnB-(SG-WHB)A,lny,
- 0.5(SK + WHB)AiIn fi,,, (14)
where
A = a,,, PlR2T2 B = b,PIRT ym=4-J2 D2=y:+p,
G = y:/D2 H = rmPmlD2 K = pm/D2 S=WZ-Q
W= -aQ/aZ= -[l-(Z-B)-‘]

Q=A
InZ+y,B+DB
2DB Z+y,B-DB
A.S. Lawn1 and E.T. van der Laan 1 Fluid Phase Equilibria 9.5 (1994) 109-121 115

The necessary (but of course not sufficient) condition for the correctness
of eqn. (14) is to ensure that in the limit of xi + 1, eqn. (14) reduces to
eqn. (5). The mixture fugacity coefficients of the VDWEOS, RKEOS and
PREOS are readily established from eqn. ( 13) because y = yrn and
B =Brn; consequently, A, In (y,) = Ai In (fim) = 0 because yrn and pm are
integer constants (see Table 1). By the same token, the fugacity co-
efficients of the listed equations in Table 1 can be established from
eqn. (13).

SPECIFIED MIXTURE RULES

The majority of the mixing rules encountered in the use of EOS for the
computation of thermodynamic properties are discussed in this section.
Let us consider an application of A, in the geometric mixture rule:

(15)
This mixture property, s,, is transformed to

In s, = 2 In f xis_!‘* (16)
(i >
Application of the A, to eqn. ( 16) yields

(17)

The summation in eqn. (17) is over all the constituents including com-
ponent i. The resulting expression for the geometric mixing rule is
established:
A, In S, = 2[(SiIS,) 1’2- l] (18)
By the same token, the linear and quadratic mixing rules follow the
reasoning of eqn. ( 17) :

A, In b, = Ai In 5 x,b, = (bi /b, - 1) (19)

(i >

A, In a, = Ai In (11 C
~X,X~a.x)=2(~x,oi~la,- 1) I (20)

where a& = a ,/a (1 - &&). Notice that eqn. (20) reduces to the
geometric mixing rule when & = 0. Also, if Q, of eqn. ( 15) is set equal to
the arithmetic average, the double summation reduces to the linear rule of
116 A.S. Lawal and E.T. van der Luan / Fluid Phase Equilibria 95 (1994) 109-121

eqn. ( 19) (Prausnitz et al., 1986). Evidently, the general case of

eqn. ( 18) can be established for the cubic mixing rule, where exponent
5 #2:

(21)

For 5 > 3, the power mixing rule can be established from eqn. (21). The
application of the A, to the SWEOS, where CX,= 2y, = 1 + 30.1, and Pm = 30,)
yields

A, In&) = 30,/( 1 + 3C0,)Ai ln(3mo,) = /?JctmAi ln(w,) (22)

Aj ln(B,) = A, ln(a,) (23)

Various mixing rules have been proposed for the calculation of om

(Varotsis et al., 1984) ; in general, they are of the rational polynomial
form:

wn = glh (24)

where

g = i XiCO,e, h = : xie, (25)

I I

where e, = b”.5 or b”.7 (Lawal et al., 1985). By applying the quotient

rule to eqn. (24) the rational polynomial mixing rule is established for
C0,:

A,lnw,=A,lng-Ajlnh=;

EOS MIXING RULES

The theme of this paper is to be able to write an expression for 4, for

any pressure-explicit EOS without resorting
of eqn. (7) and without regard to the type
describing the contribution of the component
an application of Ai in the EOS, let us consider
rule:
to the thermodynamic criteria
of mixing rules specified for
in the mixture. Therefore, as
eqn. ( 1) in the form of a mixing

(27)
A.S. Lawal and E.T. van der Laan 1 Fluid Phase Equilibria 95 (1994) 109-121 117

Mixing rules a,, a, and pm are of the form of eqn. (20) and the mixing
rule of eqn. (29) is of the form of eqn. (21); therefore the component
fugacity coefficients are readily written for eqn. (27). By using eqn. (14) as
a basis, the mixture fugacity coefficient for eqn. (27) is easily established for
the specified mixing rules:
ln(J./x,P) = (Z - 1){3[bi/b,]‘~3-2}-ln(Z -B) - Q[2&xka~~/a,
- 3(bi/b,) 1’3+2] + [S(G + 1) - WHB] -2(SG - WHB)
X (&xkaiklam) - (SK + wHB)(xkxkPik/Prn> (32)
where % =&&(l - Kik), ark =&k&&, bik =hkfi&. The
term (G + 1) of eqn. (32) results from the expression 2G + K =
G + (G + K); in accordance with the definitions of the parameters G and K
of eqn. (14), G + K = 1. The parameters of eqn. (32) (Q, S, G, I-I, K and W)
have been previously defined in eqn. (5) and ( 14). For the sake of complete-
ness, the parameters are represented by
Z + [a, + (a: + 4pm)o.53t
(33)
Z + [a, - (a; + 4/L>“.53z”

S= &B-Z-Q (34)

S(G+ 1) = & -Z-Q)[2(;;;;;1)] (35)

SG =
( 8Z~z-e)(a~~4am>
(36)

SK= (37)
(

(38)
118 A.S. Lawal and E.T. van der Laan / Fluid Phase Equilibria 95 (1994) 109-121

Notice in eqns. (32) -( 38) that yrn of eqn. (14) has been replaced by c(, in
accordance with the definition established in eqn. (3). Furthermore, any of
the mixing rules specified for eqn. (27) can be independently changed
without affecting the rest of the combining rules, as long as corresponding
terms are established for such a change from eqn. (14).

DISCUSSION OF MOLAR DERIVATIVES

The implications of eqn. (8) go beyond the results and applications in this
paper. There is indeed a functional relation between mole fractions and
mole numbers of thermodynamic property m (and their derivatives):
m =m(nl,n,, , . .) =nm(x,,x*, . . .), where m = C,ni and x, =11,/n. Such a
relation has been extensively addressed by Van Ness and Abbott (1982) and
Walas (1985): Even though x, are not all independent, this in no way
compromises the validity of eqn. (8). Physically, it is impossible to vary just
one mole fraction, because Clxi = 1. Nonetheless, the mathematical opera-
tions represented by the derivatives of eqn. (8) are correct because they are
not based on an assumption that xi are independent. Consequently, it is not
necessary, although of course it is permissible, to eliminate one of the x,
terms in Z before applying eqn. (8). Van Ness and Abbott (1982, pp.
47-48) have provided a rationalized basis for the mathematical significance
of this claim.
In principle, the thermodynamic property m can represent any of the
molar properties A, G, H, Cr,, C,, U, S, Z, u, lnf, In 4, the isothermal com-
pressibility rc, the volume expansivity /I or density p. Since the properties
represented by m are intensive, at given T and P they are functions of
composition. Therefore, eqn. (8) is generally applicable to the thermody-
namic treatment of solutions of variable composition, including those
discussed by Abbott and Van Ness ( 1992) and Mollerup and Michelsen
(1992). Although eqn. (8) (d erived by replacing mole numbers by mole
fractions) is complementary to the approaches of mole number derivatives
reported by Topliss ( 1985), Abbott and Van Ness ( 1992) and Mollerup and
Michelsen (1992), the advantage of the mole fraction approach over the
mole number derivatives is the emergence of the partial differential opera-
tor, Aj (eqn. (9)). Consequently, the use of eqn. (9) for introducing
functional modifications of mixing rules in the expression for the fugacity
coefficients makes the approach of eqn. (8) more desirable for compositions
of mixtures expressed in terms of mole fractions (Walas, 1985; p. 118) than
the approaches based on mole number derivatives (Topliss, 1985; Mollerup
and Michelsen, 1992). However, in contrast to the paper by Mollerup and
Michelsen (1992), mole fractions rather than mole numbers are the indepen-
dent variables in eqn. (8). Since EOS mixing rules directly relate to mole
A.S. Lawal and E.T. van der Laan 1 Fluid Phase Equilibria 95 (1994) 109-121 119

fractions rather than to mole numbers, derivatives with respect to mole

fractions are the most convenient for introducing functional modifications
in the expression for the fugacity coefficients. Hence, the mole fractions
approach is preferred in this paper to the mole number approach used by
Mollerup and Michelsen ( 1992).

CONCLUSIONS

The mixture fugacity coefficient is developed on the basis of the separabil-

ity of the EOS parameters and is validated by several forms of mixture
rules. The advantage of the technique lies in introducing functional modifi-
cations into the previously established mixing rules of EOS and reducing
the mathematical labor of deriving mixture fugacity coefficients. The
insight provided by A, and the logarithmic transformation of mixing rule
properties make the approach of this paper more useful than the textbook
methods.

ACKNOWLEDGMENT

The authors acknowledge the help of Betty Haire for typing the equa-
tions. The authors are grateful to the management of BP Exploration
(Alaska) for the publication of this manuscript.

LIST OF SYMBOLS

equation of state parameter

dimensionless attractive parameter
equation of state parameter
dimensionless repulsive parameter
discriminant term of the quadratic expression
fugacity of a component
number of components in a mixture
defined molar quantity
defined partial molar quantity
specific volume (or molar volume)
mole fraction
compressibility fraction ( = Pv/RT)
partial molar compressibility factor
Greek letters

cx coefficient of the LLSEOS

/I coefficient of the LLSEOS or volume expansivity
120 A.S. Lawal and E.T. van der Laan 1 Fluid Phase Equilibria 95 (1994) 109-121

y transformed coefficient ( = cr/2)

i interaction term
K interaction term or isothermal compressibility
A interaction term
A differential operator
5 exponent of mixture rule
4 fugacity coefficient for a component
0 Pitzer’s acentric factor

Subscripts

i component identity
j fixed component in the partial derivatives
k general designation of the components
m mixture

REFERENCES

Abbott, M.M., 1989. Thirteen ways of looking at the van der Waals equations of state. Chem.
Eng. Prog., 85: 25.
Abbott, M.M. and Van Ness, H.C., 1992. Thermodynamics of solutions containing
reactive species: A guide to fundamentals and applications. Fluid Phase Equilibria.,
77: 53.
Beyer, W.H., 1980. CRC Handbook of Mathematical Sciences, 5th edn. CRC Press, Boca
Raton, FL, p. 406.
de Leeuw, V.V., de Loos, Th.W., Kooijman, H.A. and de Swaan Arons, J., 1992. The
experimental determination and modelling of VLE for binary subsystems of the quaternary
system N, + CH, + C,H,, + C4Hj0 up to 1000 bar and 440 K. Fluid Phase Equilibria, 73:
285.
Harmens, A., 1977. A cubic equation of state for the prediction of N,-Ar-0, phase
equilibrium. Cryogenics, 17: 519.
Huron, M.J. and Vidal, J., 1979. New mixing rules in simple equations of state for representing
vapor-liquid equilibria of strongly non-ideal mixtures. Fluid Phase Equilibria, 3: 255.
Lawal, A.S., 1987. A consistent rule for selecting roots in cubic equations of state. Ind. Eng.
Chem. Res., 26: 857.
Lawal, AS., van der Laan, E.T. and Thambynayagam, R.K.M., 1985. Four-parameter
modification of the Lawal-Lake-Silberberg equation of state for calculating gas-conden-
sate. Paper SPE 14269 presented at the SPE Annual Meeting, Las Vegas, NY, 22-25
September.
Lewis, G. N., 1901. The law of physico-chemical change. Proc. Am. Acad. Arts Sci., 37(3):
49.
Mansoori, G.A., 1986. Mixing rules for cubic equations of state. In: K.C. Chao and R.L.
Robinson (Eds.), Equations of State; Theories and Applications. ACS Symposium Series
300, Washington, DC, p. 315.
Michelsen, M.L. and Mollerup, J.M., 1986. Derivatives of thermodynamic properties. AIChE
J., 32: 1389.
A.S. Lawal and E.T. van der Laan 1 Fluid Phase Equilibria 95 (1994) 109-121 121

Modell, M. and Reid, R.C., 1983. Thermodynamics and its Applications, 2nd edn. Prentice-
Hall, Englewood Cliffs, NJ, p. 183.
Mollerup, J.M. and Michelsen, M.L., 1992. Calculation of thermodynamic equilibrium
properties. Fluid Phase Equilibria, 74: 1.
Olivera-Fuentes, C., 1991. Multicomponent fugacity coefficients and residual properties from
pressure-explicit equations of state. Chem. Eng. Sci., 46: 2019.
Peng, D.Y. and Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng.
Chem., Fundam., 15: 59.
Prausnitz, J.M., Lichtenthaler, R.N. and Gomes de Azevedo, E., 1986. Molecular Thermody-
namics of Fluid-Phase Equilibria, 2nd edn. Prentice-Hall, Englewood Cliffs, NJ.
Redlich, 0. and Kwong, J.N.S., 1949. On the thermodynamics of solutions. V. An equation
of state. Fugacities of gaseous solutions. Chem. Rev., 44: 233.
Schmidt, G. and Wenzel, H., 1980. A modified van der Waals type equation of state. Chem.
Eng. Sci., 35: 1503.
Smith, J.M. and Van Ness, H.C., 1975. Introduction to Chemical Engineering Thermody-
namics, 3r edn. McGraw-Hill, New York, p. 60.5.
Szarawara, J. and Gawdzik, A., 1989. Method of calculation of fugacity coefficient from
cubic equations of state. Chem. Eng. Sci., 44: 1489.
Topliss, R.J., 1985. Techniques to facilitate the use of equations of state for complex
fluid-phase equilibria, Ph.D. dissertation, The Univeristy of California, Berkeley.
van der Waals, J.D., 1873. On the Continuity of the Gaseous and Liquid States, (Leiden,
1873). English translation by R. Threlfall and J.F. Adair in Physical Memoirs, Physical
Society of London, Vol. 1, Part 3, 1890.
Van Ness, H.C. and Abbott, M.M., 1982. Classical Thermodynamics of Nonelectrolyte
Solutions. McGraw-Hill, New York, p. 43.
Varotsis, H., Stewart, G., Todd, A.C. and Clancy, M., 1984. The phase behavior of systems
comprising North Sea reservoir fluids and injection gases. Paper SPE/DOE 12647
presented at the SPE/DOE Enhanced Oil Recovery Symposium, Tulsa, 15- 18 April.
Walas, SM., 1985. Phase Equilibria in Chemical Engineering. Butterworths, Stoneham, MA,
pp. 118, 121.