Fluid Phase Equilibria,

3 (1979) 255-271
@ Elsevier Scientific Publishing Company,

255
Amsterdam

- Printed in The Netherlands

NEW MIXING RULES IN SIMPLE EQUATIONS OF STATE FOR

D E_QUILjIlRIA OF STRONGLY
REPRESENTING
VAPOUR-LIQU
,:
NON-IDEAL MIXTURES *
c I
i
MARIE-JOSE
Institut

HURON and JEAN VIDAL

Franpzis

(Received

du Pktrole,

December

1 et 4, Avenue

20th, 1978; accepted

de Bois-Pr&u,

92502

Rueil-Malmaison

(France)

in revised form May 18th 1979)

ABSTRACT
Huron, M.-J. and Vidal, J., 1979. New mixing rules in simple equations of state for representing vapourliquid
equilibria of strongly non-ideal mixtures. Fluid Phase Equilibria,
3: 255-271.
Good correlations of vapour-liquid
equilibria can be achieved by applying the same
two-parameter cubic equation of state to both phases. The results primarily depend on the
method used for calculating parameters and, for mixtures, on the mixing rule. True parameters are the covolume b and the energy parameter a/b. For this latter one, deviations from
a linear weighting rule are closely connected to the excess free energy at infinite pressure.
Thus any mixing rule gives a model for the excess free energy, or any accepted models for
this property can be used as mixing rules.
From the above, an empirical polynomial mixing rule is used for data smoothing and
evaluation, while for practical work a local composition
model is used. The mixing rule
thus obtained can be reduced to the classical quadratic rule for some easily predicted
values of the interaction energies. For highly polar systems, it includes three adjustable
parameters. Using literature data, the new mixing rule is applied, in the low and high pressure range, to binary mixtures with one or two polar compounds,
giving good data correlation and sometimes avoiding false liquid-liquid
immiscibility.

INTRODUCTION

When applied to both vapour and liquid phases, cubic equations of state
can be used to calculate phase equilibria. Pure-component parameters are
evaluated from critical conditions and vapour pressure data. To obtain the
mixture parameters, classical mixing rules are used, and good results are obtained for non-polar gases (Soave, 1972; Peng et al., 1976; Robinson et al.,
1977). The binary parameters which appear in the mixing rules can be predicted by various combining laws (Hicks et al., 1975) or fitted to experimental data. In this way, the application range can be extended (Huron et al.,

Part of this article was presented

at the Chisa Congressin

Prague, August 1978.

256

1977; Asselineau et al., 1978a; Graboski et al., 1978) to slightly polar mixtures.
However, classical mixing rules imply a quasi-regular behaviour (Vidal,
1978) and, unless a thorough revision is made, the method cannot be applied
to polar mixtures. It has been proposed that the value of the pure-component
parameters be modified (Wenzel et al., 1971; Deiters et al., 1976; Wenzel et al.,
1978). However, the close relation existing between excess Gibbs energy and
mixing rules led us to the problem of evaluating mixture parameters, and this
paper is devoted to mixing rules.
EXCESS GIBBS ENERGY

FROM THE EQUATION

OF STATE

As pointed out by Smith and Van Ness (1975), there are three fugacity
coefficients, one for a pure component, cp;, one for the solution, cp, and one
for a component in solution, Cpi.They are related to Gibbs energy and chemical potential by their definition equations:
RTln&=+f-gi*=!

(~r-y)dP
0

RTln~=g-g=~p(v-~)dP
0

RTlnIpi=~i-&=pi-pj=J

(ci-y)dP
0

The Gibbs energy of the pure components

by:

and of the mixture are related

g = iz Xi&j* + RT In

(4)

xi)

in the ideal gas state, and by:

n
g = 2 Xi&r + RT In Xi) + gE

(5)

in the real mixture.

By substituting eqns. (l), (2) and (4) into eqn. (5), we obtain the general
equation relating excess Gibbs energy to fugacity coefficients.
gE=RT[lnp-&xilnlpfl

(6)

i=l

The expression for the fugacity coefficients

depends on the equation of

267

state that is used and is the same for cpr and cp:
~pf= F(T, P, u;, aii, bii, e-e)
cp = F(T, P, u, a, b)
So the various expressions we shall deduce from eqn. (6) will depend on the
equation of state, but not on the mixing rules.
We shall first apply eqn. (6) to the modified Redlich-Kwong
equations of
state :
(u -

b) = RT

in which parameters (I and b are solely composition

dent. The fugacity coefficient of a pure component
pressed as:

and temperature depenor of a mixture is ex-

(8)
and from eqn. (6) we obtain:

(9)
RELATION

BETWEEN EXCESS GIBBS ENERGY

AND MIXING RULES

The relation between the excess Gibbs energy gE and the mixing rules
implicit in the a and b values is not obvious. At this step, we consider the
limiting value of gE at infinite pressure. If at infinite pressure the excess
volume is not zero, the limit of gE is infinite. Thus, as a necessary condition
to obtain a finite limit, we apply the common linear mixing rule for volume
parameter b :
b = 2

biixi

i=l

From eqns. (7), (9) and (lo),

equation for g!Z is:
In 2

it can easily be shown (see Appendix

1) that the

(11)

We see that the gz value and the excess value of the energy parameter a/b

258
are proportional
. So the value of the excess Gibbs energy gz will correspond
to the choice of mixing rule. As an example (Vidal, 1978) we give the classical
quadratic mixing rule:

2 2 QijXiXj

a =

i=l

associated
CZij

(12)

j=l

with the combining

rule:
(13)

(a$Zjj)1'2(1hij)

and with the linear law (10) for parameter b leads to a quasi-regular
For a binary system, for example, we obtain:
&

= (In 2) b&@st(%

6~)~ + 2

mixture.
(14)

b&,6,1

with

4i

Xibii
=b

EIowever,

ai=

and
eqn. (11)

v--~aiilbii
bit

(15)

can be used to produce

a mixing

rule for parameter

a
(17)

from the chosen excess Gibbs energy at infinite pressure. We do this in this
paper.
When dealing with equilibrium problems, the fugacity coefficients
for the
components in solution must be evaluated. By applying classical thermodynamics and mixing rules (10) and (17), we obtain:
Inv,=-_ln(P(ii*))

+$(%-I)

where the activity

In yi_

= &

[ g

coefficients
n a&
+,zz(Aij--Xj)
j

--(k-s)
at infinite

In(F)

pressure are calculated

(18)
by:

The pure-component
parameters will be determined from stability
and vapour pressure values, as explained in Appendix
2.
NEW MIXING

(19)
conditions

RULES

In vapour-liquid-liquid
equilibrium investigations, we meet two kinds of
problems: (1) data smoothing, data and model evaluation; and (2) in the
common practice of the chemical engineer, equilibrium predictions from a
minimum amount of data. We now consider briefly the first of these.

259

Polynomial

mixing

rule

For data smoothing and evaluation, we look for great flexibility in the
mixing rule. In the low pressure range, a Redlich-Kister
polynomial expansion
of the excess Gibbs energy is often applied to binary systems:

gE = RTxlxZ

mfO

A,(xl

(20)

~2)~

Applying the same equation to the excess Gibbs energy at infinite pressure,
from eqns. (10) and (17) we obtain:
a = (z,b,,

+ x,b,,)

x1 p

+x2
11

u22
b22

-__

RT

In 2

x1x2

A,n(x,

m=O

-x2Y

(21)

Such a mixing rule is applied, as an example, to the carbon dioxide(l)ethane(2) system (Ohgaki et al., 1977) at 283.15 K. The pressure range is
20-50 atm. The polynomial parameters, A,,,, will be determined by minimizing the objective function:

where P is the equilibrium pressure calculated for the experimental values of

T and X, and P,, is the experimental pressure. According to Peneloux et al.
(1975), the weighting factor up is calculated by:_,
2_
UP -

(uP,ex)2
+

[(E),%J2+[(E),UTJ2
:

(22)

where UP.,,, ux,ex,uT,ex arethe experimental uncertainties associated with

pressure, composition and temperature measurements, respectively. :
.i ;From Ohgaki et al. (1977), we took:
up = 0.01 atm,

ur = 0.01 K,

u, = 0.002

The data correlation with the Redlich-Kister

equation for gE improves when
the number of parameters is increased to a four parameter expansion. A slight
underestimation of the experimental uncertainties u~,~_, ur ,ex, uT,ex appears
in the results:

but the pressure deviations:

260
A P-Pexp (atm.)

45.
l*=
'.

m
.

.- .
.

-x1

-95
t
4 P-P,,(atm.)

0.5 -

Fig. 1. Correlation of the carbon dioxide(l)-ethane(2)

mixing rule; X , classical mixing rule.

system. l, proposed polynomial

are small and random, and because of the great flexibility of the model they
can be considered as an evaluation of experimental data scattering. For example, after fitting to the same data (Ohgaki et al., 1977) the interaction
parameter kij involved in classical mixing and combining rules (12) and (13),
the results obtained:
ZP = 0.48 atm

have to be considered with reference to the limit previously obtained (0.1 atm).
Furthermore, as shown by Fig. 1, the deviations in pressure are not random,
because of the wrong skewness of the excess Gibbs energy associated with the
classical mixing rule.
Local-composition

mixing rule

In common practice, a chemical engineer is concerned with models for

predicting vapour-liquid equilibria from a minimum amount of data, with a
minimum set of parameters. For this purpose, classical mixing and combining
rules (12) and (13) are advantageous, since only one interaction parameter klZ
has to be known to obtain good correlation for many binary mixtures. Thus

261

we look for a new mixing rule which, when only non-polar compounds are
present, can be reduced to the classical one by a straightforward choice of
parameters, but which can provide more flexibility if necessary. The localcomposition concept (Wilson, 1964) has led to many powerful models of the
liquid phase (Vetere, 1977). The Scatchard-Hildebrand
theory can be established, among other hypotheses, by considering only the interactions between
first-neighbour molecules (interactions between more than two molecules and
influence of long-range molecules are neglected), and by assuming that the
first-neighbour interaction occurrences are proportional to the overall volume
fractions (Moelwyn-Hughes, 1961). Therefore we deduce local compositions
tji and Eii, which give the distribution of molecules j and i about the central
molecule i, from overall volume fractions $j and @i :
tji _ @j exP(--cYjigji/RV
Eji

(23)

@i exP(-ajigii/RV

The volume fractions introduced here, and already defined by eqn. (15),
must be evaluated at infinite pressure since they will be applied to the g!
formulation. They are weighted by Boltzman factors, including interaction
energies between unlike (gji) and like (gii) molecules and, as in the NRTL
model (Renon, 1968), a non-randomness parameter eji. The value of the excess Gibbs energy at infinite pressure is then calculated in exactly the same
way as in the NRTL equation, and the resulting equation is the same:

?JXjGjiCji

g2 =

gxij=l

(24)

i=l
2
k=l

XhGhi

with
(25)

Cji = gji - gii

and
Gji = bj

exp(-aji&)

(26)

The only difference from the classical NRTL model is the definition of the
local composition as corrected volume fractions, which leads to the introduction of the volume parameter bj in the calculation of Gji. From the choice of
such a model for the excess Gibbs energy at infinite pressure, the mixing rule
is deduced by applying eqn. (17):

n
==b

xx1

s-1
bii

i=l

Xj

GjiCji

j=l

(27)

In 2
~
k=l

XkGki

262

An exact reduction to the classical mixing and combining rules (12) and
(13) can easily be obtained by the following calculation of the coefficients:
Lyij= 0
gii = -(In

2)-i
ii
(29)

where kij is the interaction parameter involved in the combining rule (13).
Owing to the zero value of the non-randomness parameter, local compositions are equal to volume fractions and the excess Gibbs energy at infinite
pressure is quasi-regular. The iriteractions energies can then be calculated
from the parameters of the equation of state. So the new mixing rule (27) contains, as an optional possibility, the classical rtfle. When applying the mixing
rule to vapour-liquid equilibria calculations, we shall consider three possibilities. In the first, the parameter 01is zero and we apply eqns. (24) to (29). It is
the classical mixing rule, and the interaction parameter will be adjusted to
experimental data. In the second, eqns. (24) to (29) will still be applied, but
both kij and aij will be determined from experimental data. We found by
experience that data correlation can be greatly improved in this way. Finally,
we can apply eqn. (27), in which the three adjustable parameters will be Cij,
Cji and ii for a binary mixture.
As in the classical NRTL model, the skewness of the excess Gibbs energy
versus composition curve mainly depends on the C, values, and flatness is
increased by high values of OL,thus providing great flexibility in the equilibrium correlation and preventing false liquid-phase splitting.
APPLICATION

TO VAPOUR-LIQUID

EQUILIBRIUM

CORRELATION

We applied the local-composition mixing rule (27) in the low and high pressure ranges. A phase equilibrium algorithm, constructed to avoid the trivial
solution occurring near the critical point (Asselineau et al., 1978b), was used.
Parameters were adjusted by minimizing the function:
NT

SQ F 5
N=l

(P-P,,);

+ c
N=l

(yr -y;,,,)&

=SQP+SQY

(39)

where P and yi are the calculated pressure and vapourphase composition. By

minimizing the function S&P instead of the function SQ, nearly the same
results would be obtained, since SQY is negligible compared to SQP in most
cases. Table 1 gives the results. From the mean deviations in pressure:

263

it can be seen that data correlation can be greatly improved by the local-composition mixing rule, and adjusting only the interaction parameter and the
non-randomness parameter (second option in the mixing rule) gives quite
good results for most systems. Furthermore, it must be emphasized that the
classical mixing rule has a strong tendency towards false phase-splitting predictions. For example, as shown by Fig. 2, the behaviour of an acetone-water
P&m

425

0.50

Q75

Xl,Yl

I
0

425

w5

Xl,Yl

P/atm

P/atm

t = 25oT

0,25

950

0*75

J
WY1

Fig. 2. Correlation of acetone( 1 )-water( 2) vapour-liquid

equilibria. - - - , classical mixing
proposed local
rule with a fitted parameter kl2 (klz values are given in Table 1); mixing rule with three fitted parameters (see Table 1); 0, experimental boints (Griswold,
1952).

Ref.

Berro,
1974

Tasic,
1978

Griswold,
1952

System

Methanol-1,2dichloroethane

Acetonecyclohexane

Acetonewater

Temperature

l-4

5-12

15-30

39-67

150

209

250

0.15-0.35

25

100

0.31-0.65

Pressure
range
(atm)

50

(G)

NT

Fitted
parameters

13

25

17

22

23

Cl29 Cal* a

k12
&?,a

c12, c21, a

kg
k12>o

k12
kl2, a
Cl% c21, a

h2
kl2r a
Cl% c21, a

c12, c21, Q

k12
+z, o

kl,? a
Cl,, c21, @

30 h2

NT

LY = {[ c (Yl -Yl,ex)~l/NT~o*5
N=l

Correlation of vapour liquid equilibrium data

TABLE 1

-0.087
+0.001

-0.128
-0.022

-0.165
-0.063

-0.202
-0.108

0.112
0.093

0
0.269
0.429
0
0.277
0.416
0
0.293
0.422
0
0.281
0.461

0
-0.445
-0.835

0.570
0.471

0.227

CI

0.084

k12

73011

71261

67446

61798

24568

58849

39743

38961

34579

14768

60768

(atm
cm3/mo1e)

(atm
cm3 /mole)

17833

c21

Cl2

0.36
0.06
0.05
0.97
0.10
0.04
2.17
0.21
0.16
2.80
0.44
0.24

0.016
0.004
0.001

0.014
0.005

0.049

(atm)

LJ

0.08
0.01
0.01
0.05
0.01
0.01
0.05
0.01
0.01
0.04
0.01
0.01

0.049
0.012
0.004

0.07
0.02
0.01

AY

Propaneethanol
GomezNieto,
1978

25

Ohgaki,
1976a

co2

25

Ohgaki,
1976b

Ethanemethyl
acetate
Methanol-

11

12

6-41

6-47

13-56

101.85

126.85

151.85
11

12

3-27

76.85

16

10

16

l-16

5-80

7-59

4-38

4-39

30-50

51.85

40

25

Ohgaki,
1976h

Ethaneacetone

10

Ohgaki,
1977

COs-ethane

42
kl2,a

kl2va
Cl29 c21,a
h2
kl2.a
Cl29 CZlt~

kl2
kl2,a
Cl29 c21>a
h2
kl2,a
c12> c21,a
h2

km
Cl27 c21,a
kl2
Cl, C21,Q

kl2
kl2,a
Cl% C21ra

h2
kl2ra
Cl% c21, a

Cl23 G?l%~

h
km Q!

0.016
0.039

0.028
0.060

0.027
0.063

0.026
0.056

0.035
0.070

0.062

0.051

0.129
0.153

0.142
0.158

0.139
0.2

0.102

0.124
0.731

0.117
1.112

0.078
0.972

0.070
0.740

0
0.043
0.437
0
0.730
0
0.652

0
0.025
0.476

0
0.673
0.638

26525

53826

41604

57644

31884

48457

47118

47933

18257

6929

27879

24938

28717

14120

11940

15192

21130

19910

0.65
0.48
0.14
0.66
0.48
0.21
1.18
0.97
0.41
0.76
0.14
0.12
0.90
0.76

1.23
0.59
0.51
2.68
0.50
2.33
0.71

1.02
0.66
0.52

0.34
0.16
0.15

0.01
0.02
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.03
0.02
0.02
0.04
0.04

0.001
0.001
0.003
0.001

0.004
0.002
0.002

0.001
0.002
0.001

0.005
0.006
0.005

266

system cannot be correlated by the quadratic mixing rule since a large miscibility gap would be predicted. On the contrary, the local-composition
model can
be applied with good results, up to the critical range.
DISCUSSION

AND CONCLUSION

Calculating vapour-liquid
equilibria by applying the same equation of
state to both phases was discussed by Van der Waals. When using such a method, choosing the equation of state, the choice of the pure-component
parameters and the choice of the mixing rules are decisive steps. The more constants
the equation of state has, the more mixing rules are required, and the more
data are required for evaluating the pure-component
parameters. Thus twoparameter cubic equations of state are often preferred. Proposed by Berthelot,
adopted by Van der Waals and now extensively used, the quadratic mixing
rule, as applied to the attraction parameter, is strongly supported by the
:
results obtained in phase equilibria predictions for non-polar or slightly polar
systems. Furthermore, the existing relation between a, b and the second virial
coefficient:
B = 2 5 BijXiXj = b i=l j=l

(a/RT)

and the commonly accepted quadratic law for B imply a quadratic law for a.
When applying the mixing rule (27) for parameter a, the quadratic law for the
second virial coefficient B will not be obeyed. However, in the high density
range and for polar mixtures, the experimental behaviour of excess Gibbs
energy does not obey the law implied by the classical mixing rule. Our method for deducing a mixing rule from a model of excess Gibbs energy is highly
empirical, but is consistent with the vapourliquid
equilibrium calculations.
The Soave equation of state is used here with new mixing rules for parameter a. The close connection found between the energy parameter (a/b) and
the excess Gibbs energy g: can be extended to other cubic equations of state
having the form:

p=

- RT
u-

a(T)
-

(31)

b -9(u)

If the roots of $J(u) are proportional

written:
G(v) = (u + bh,)(u

FyLgxi%a]^
i=l

b, that is if G(u) can be

+ &AZ)

in which X1 and As are numerical

gz=-

to parameter

iI

(32)
constants, then the equation

for g? is:

(33)

267

with
1
Iz = AZ - A1 In

if h2 # hi

Eqn. (33) is valid for the following

Harmens (1978)

A = -&ln(fs));

Peng and Robinson (1976)

Redlich-Kwong

two-parameter equations of state:

A =

and Soave (A = In 2); and Van der Waals (A = 1).

But eqn. (33) does not apply to the three-parameter equations of state of
Clausius, Fuller (1976), Horvath and Lin (1977) and Usdin and McAuliffe
(1976), for which the roots of Q(u) are not proportional to b. For these last
equations, we need to set mixing rules for two parameters in order to be
able to calculate the third one from gz .
Like the choice of a mixing rule, the choice of a model for the excess Gibbs
energy is difficult, as shown by several attempts in the litterature. We used
two expressions, depending on the problem.
It would be attractive to apply the polynomial mixing rule to a consistency
test by comparing calculated and experimental vapour compositions. In the
low pressure range, the influence of the polynomial mixing rule on the density
of the vapour phase is slight, and we obtained the same results by using the
standard method (Redlich-Kister
excess Gibbs energy, reference fugacities in
the liquid phase, virial equation of state for the vapour phase) or by applying
the straightforward technique of the polynomial mixing rule (21). In a higher
pressure range, however, such a method would be questionable since the
calculated vapour phase compositions are sensitive to the vapour density
evaluation (Won et al., 1973). On the whole, our results did not show any
systematic discrepancy between experimental and calculated vapour phase
composition, but we shall not use them as a consistency test and we shall
reserve the polynomial mixing rule for evaluating data scattering.
Application of a local-composition
(NRTL) model to the excess Gibbs
energy at infinite pressure was first considered by Chaudron et al. (1973).
However, the proposed method used reference fugacities and, together with
the NRTL model, a mixing rule was used for the equation of state, which was
applied to the calculation of the fugacities in the vapour phase, for the

Poyinting correction and for the reference fugacities. Although thermodynamically more sound, this method requires more parameters and does

268

not use the same model for calculating vapour phase fugacities and liquid
phase fugacities.
If we decide to apply the same model to both phases, the implicit relation
between mixing rule and excess Gibbs energy has to be considered and can be
used.
ACKNOWLEDGEMENTS

Thanks are extended to Professor Peneloux (University of Marseille) and to

our colleague Dr. Asselineau for helpful discussions and suggestions.
LIST

a, b
B
C
g

k
;P
NT
P
R

OF SYMBOLS

Redlich-Kister coefficient
parameters in the equation of state
virial coefficient
parameter in the mixing law
Gibbs free energy or interaction energy parameter
interaction parameter associated with a
number of components in the mixture
number of parameters
number of experimental points
pressure (atm) 1 atm = 1.01325 X 10 Pascals
perfect gas constant = 82.0562 atm cm3 K-l mol-
mole1 K-l
function to be minimized
temperature (K)
molar volume ( cm3/mole)
molar fraction
non randomness parameter
activity coefficient
solubility parameter
Kronecker delta
deviation in pressure
deviation in mole fraction
numerical constants
local composition
weighting factor
fugacity coefficient
volume fraction
volume function

Superscripts or subscripts
C

critical property
excess value

or 8.3143

269

experimental value
component identification
experimental point
ideal state
pure component
at infinite pressure
an overbar denotes a partial molar property

ex
i, j
N
*
00
-

APPENDIX

1. LIMIT

OF EXCESS

GIBBS

ENERGY

AT INFINITE

PRESSURE

From eqn. (9), we write the excess Gibbs energy as

gE=$+&+g3E
where

when P + 00, u + b, vr + bs and from the equation of state (7) we see that:
I

P(v-Wcl_

4v-b)

RT

RTu(u + b)

The second term g! can be written

--& _P(u-bb)
RT

RT

+
RT

or

SZ _P(V-bb)_~x_P(uf-bi,)+
-I
RT

RT

RT

i=l

Pb

&,Pb,

RT

i=l

and, from the value of the limit of [P(u see that:

E+O
412

if

b = 2

i=l

xibii

b)]/RT,

RT

and [P(uf - bii)]/RT,

we

270

So gg has the same limit as gt , the value of which is given by eqn. (11).
For the other equations of state mentioned in discussion, the limit is established in the same way.
APPENDIX

2. DETERMINATION

OF PURE-COMPONENT

PARAMETERS

In the equation of state (7), parameter bii was considered as independent

of temperature, and we applied Soaves correlation (Soave, 1972) to parameter aii:
Uii=

Cr,i[l + mi(l -m)]

The values of U,+ and bCi are determined from critical conditions:
1
=ci = 9(21/a

1)

R2Zi

pci

bi* = bci =

213~1%

pci

Soave correlated value mi with an acentric factor. We preferred to apply

the vapour-liquid equilibrium condition to the pure components, and to
evaluate parameter Uii, for a given subcritical pure component i, from its
vapour pressure. The values of aii and mi were determined from one point on
the vapour pressure curve. In the ensuing correlation of mixture data, to
avoid any discrepancy which can be attributed to the pure-component parameters, the vapour-pressure point was chosen in the same temperature range as
the mixture data.
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