FIuid Phase Equilibria, 65 (1991) 111-133

Elsevier Science Publishers B.V., Amsterdam

111

Simultaneous representation of excess enthalpy

and vapor-liquid equilibrium data by the NRTL
and UNIQUAC models
Ya$ar Demirel

and Hatice

Gecegiirmez

Faculty of Art and Sciences, University of Cukurova 01330 Adana (Turkey)

(Received

May 29, 1990; accepted

in final form February

6, 1991)

ABSTRACT
Demirel, Y. and Gecegijrmez,
vapor-liquid
equilibrium
Equilibria, 65: 111-133.

H., 1991. Simultaneous

representation
data by the NRTL and UNIQUAC

of excess enthalpy and

models.
Fluid Phase

Using data for excess Gibbs energy, g, and enthalpy of mixing, hE, temperature-dependent parameters of the NRTL and UNIQUAC
models have been estimated for 44 systems of
binary mixtures. Thirty-three of them include data for gE and hE at more than one different
isotherm.
The estimated
parameters
were later tested by predicting
the total pressure,
vapor-phase compositions
and gE and hE data simultaneously
and representing
the effect of
temperature
on such data. System-dependency
of the models, non-uniqueness
in the parameters and the possibility of predicting partial miscibility for completely miscible non-ideal
mixtures have been investigated.

INTRODUCTION

The NRTL (Renon and Prausnitz, 1968) and UNIQUAC

(Abrams and
Prausnitz, 1975) models have found extensive use in the correlation
and
prediction of fluid phase equilibria and chemical process calculations,
such
as distillation.
They can predict the partial miscibility and are easily extendable to multicomponent
mixtures using the parameters
obtained from
binary data alone. In a recent study, Cairns and Furzer (1988) pointed out
that the limitations of these models must be considered in the design and
retrofit of distillation columns, although there would appear to be a major
difficulty in selecting the best model, since the choice may be system-dependent. This aspect needs to be investigated further in order to gain a critical
and lasting evaluation on the behavior of the models.
037%3812/91/$03.50

Q 1991 Elsevier Science Publishers

B.V.

112

Renon and Prausnitz (1969) provided charts for estimating the binary
adjustable energy parameters
of the NRTL model from limiting activity
coefficient data and from mutual solubilities. They suggested that, depending on the chemical nature of a mixture, a value of aij must be chosen. But
as Tassios (1976) points out, the selection of proper values of clljj is
ambiguous and difficult to apply, and the NRTL model performs best when
the value of Y;~is obtained by regression of the available experimental data.
Flemr (1976) and McDermott and Ashton (1977) pointed out the theoretical
inconsistency of the NRTL and UNIQUAC models and concluded that they
should be treated only as empirical. Later Panayiotou and Vera (1981) and
Iwai and Arai (1982) have discussed the statistical thermodynamic
derivation of the UNIQUAC model.
Tassios (1979) showed that multiple roots are possible for positive deviations from Raoults law for the NRTL model. However, he concluded that
when (Y~,is allowed to vary, the multiplicity does not seem to represent a
problem.
Hanks et al. (1978) have performed a parametric analysis of the NRTL
model to determine appropriate limits to its ability to represent gE and hE
data simultaneously.
This analysis showed that the NRTL model is not
capable of correlating both gE and hE data for any system in which the
value of hE exceeds a certain limit, A similar study performed by Demirel
and Gecegiirmez (1989) indicates that the UNIQUAC
model has a similar
property. This limitation can be overcome by treating the parameters of the
models as functions of temperature and using experimental heats of mixing
along with vapor-liquid
equilibrium (VLE) data (Murthy and Zudkevitch,
1979; Demirel and Gecegbrmez, 1989).
The NRTL and UNIQUAC models have a moderate built-in temperature
dependence.
However, Murthy and Zudkevitch (1979) suggest that relying
on the NRTL model for representing
the effect of temperature
on the
activity coefficients can be unreliable. Both of the models perform better
when the parameters vary with temperature
as suggested in the literature
(Anderson and Prausnitz, 1978; Demirel and McDermott, 1984). Pablo and
Prausnitz (1988) suggest that for the NRTL model a strong temperature
dependence
is required to describe the coexistence curve in the critical
region.
In this study, temperature-dependent
parameters
for the NRTL and
UNIQUAC
models were estimated using gE and hE data simultaneously,
and the accuracy in predicting gE, VLE and hE data by the equations has
been investigated for various types of mixture including alcohols, carboxylic
acids, water and esters.

113
HEAT OF MIXING

The rate of change of excess Gibbs energy, and hence the activity
coefficients,
y,, with respect to temperature
is proportional
to the excess
enthalpy and is given by the Gibbs-Helmholtz
equation

-=- ahEm
1
hE
T2

aT

0)

P,x

Nagata and Yamada (1973) and Nagata et al. (1973) have shown that the
NRTL model whose parameters
are assumed to be expressed by a linear
function of temperature
is capable of representing both VLE and hE data
with a single set of parameters. Renon and Prausnitz (1968) also assume that
the NRTL parameters change with temperature in a linear way.
g,, - g,, = ci + c2( T - 273.15)

(2)

g,, - g,, = c3 + c,( T - 273.15)

(3)

ai2 = c5 + cg( T - 273.15)

With the NRTL
becomes
hE

parameters

(x,x2Gd

(Xl

(hxl)

X2G2, >

(XlX2GlZ
+(

x2 +

(XI
I

w,2)

given in eqns. (2)-(4)

l-

(12712X2
(x2

(c1

273

+I,)

>

( cg -

15~

x2G21)

the enthalpy

(4)
of mixing

1
1

r,:X,C,RT2
Xl + XzG21

273.15~~) + $2y;,,2
1

12

(5)

where
G2,

exp( -

a12721)

Gl2

exP( -

y12712)

721 =

(g21

&J/RT

712 =

(g,,

g22VRT

Abrams and Prausnitz (1975) state that when both VLE and liquid-liquid
equilibrium (LLE) data are used to obtain the UNIQUAC parameters, they
appear to be a smooth function of temperature. However, this is not the case
for mixtures containing
hydrogen bonding, such as water and alcohols
(Anderson
and Prausnitz, 1978; Murthy and Zudkevitch,
1979). In the
present study, the effect of temperature
on the characteristic
energies is
expressed as
azl = d, + d/T

(6)

al2 = d, + d,/T

(7)

114

These are the expressions also used by Anderson and Prausnitz (1978). With
the UNIQUAC parameters given in eqns. (6) and (7), the enthalpy of mixing
becomes

where
72; = exp( -%1/T)
G = exp( - +/T)
8j = Xjqi/Cxiqi
The UNIQUAC
model contains pure-component
structural parameters
r
and q. Anderson and Prausnitz (1978) modified the UNIQUAC
equation
slightly and introduced new values of surface parameters,
q, for alcohols
and water to be used in the residual part of the equation.

ESTIMATION

OF PARAMETERS

In estimating the temperature-dependent

parameters, data for gE and hE
were used simultaneously.
The following objective function, which was also
used by Nagata and Yamada (1973), was minimized:

where n and m are, respectively, the number of experimental

gE and hE
data points at a specified isothermal
temperature.
N is the number of
isothermal system temperatures
for the gE data and M is that for the hE
data. For minimizing the function F, a package program called MINUIT
(James, 1978) was used. The MINUIT program performs minimization
and
analysis of the shape of a multiparameter
function, and incorporates
the
Fletcher and Simplex techniques. Nagata and Yamada (1973) suggest that
the Simplex method is one of the most effective parameter seeking methods.
Each technique may be used alone or in combination
with the others,
according to the behaviour of the function and the requirements of the user.
Some global logic is built into the program so that, if one of the techniques
fails another technique is automatically
called to make another attempt.

115

An analytical method due to Tassios (1976) is used to determine the

ability of the estimated parameters
to predict the phase splitting. This
consists of the following steps:
(1) Regress the gE and hE data to obtain the temperature-dependent
parameters of the models.
(2) Introduce these values into the following expression for G:

T.P

(3) Determine the value of xi = x0 for which G

value, by solving the following equation:

assumes

its minimum
/

1,,

0
(11)
=
T,P
(4) Insert the value of x1 into eqn. (10) and determine the value of G. If
G > 0, no partial miscibility will be predicted for the estimated values
of the parameters. If G < 0, partial miscibility will be predicted.
G

RESULTS AND DISCUSSION

Using data for gE and hE, temperature-dependent

parameters
of the
NRTL and UNIQUAC models were estimated for 44 binary systems. These
mixtures include hydrocarbon,
ester, alcohol, ketone, carboxylic acid and
aqueous components in various combinations. Only the values of the parameters c5 and cs, in the NRTL model, are forced to change between 0.1 and
0.7, and - 0.1 and 0.2, respectively. The estimated parameters for the NRTL
and UNIQUAC models and variances of the fit, u, are given in Tables 1 and
2, respectively. The variance of the fit is obtained from
u=
(ffni

NP
1

Ii4
(WNP)

)
02)

Here CNni and Cmi are the total number of data points for gE and hE,
respectively, while NP is the number of parameters. The value of (I provides
a measure of how well gE and hE data are represented simultaneously
by
the NRTL and UNIQUAC
models. Temperature-dependent
UNIQUAC
parameters
for the first 24 systems were given elsewhere (Demirel and
Gecegormez, 1989).

25-45

25-50

25-45

25-45

25-55

25-55

25-55

25-55

25-45

2. Methyl acetate(l)cyclohexane(2)

3. Methanol(l)ethyl acetate(2)
4. Ethanol(l)ethyl acetate(2)
5. 2-Propanol( l)ethyl acetate(2)
6. l-Propanol(l)ethyl acetate(2)
7. Ethyl formate(
methanol(2)
8. Ethyl formate(l)ethanol(2)
9. Ethyl formate(l)1-propanol(2)
10. Ethyl formate(l)2-propanol(2)

25-50

Twin- T&w.
(C)

1. Methyl acetate(l)benzene(2)

System

- 124.44
1.84
- 467.26
- 11.75
717.79
- 3.26
705.93
3.47
568.81
- 2.14
617.11
- 2.52
166.92
- 4.70
309.02
- 4.07
357.15
- 1.55
405.62
- 2.27
383.90
- 3.30
440.42
- 3.86
386.82
- 2.36
766.33
12.72
738.33
- 1.93
788.27
- 1.84
355.10
-0.98
378.16
- 2.28
523.00
1.25
465.68
1.22
563.42
- 0.62
644.69
- 1.45
565.59
- 1.16
615.92
- 1.55

0.1507
0.5800
0.0762
- 0.4730
0.4704
0.1582
0.5027
0.2106
0.5931
-0.1185
0.5999
- 0.1243
0.2538
0.2909
0.1608
0.1986
0.5173
-0.3895
0.5685
-0.1994
0.5307
- 0.2120
0.5998
0.3554

g-1,

(cal mol-

::a1 mol-
K-)

C5

C3
(cal mol-)

CI
(cal mol-)
K-)

Temperature-dependent parameters of the NRTL model and the variation of the fit

TABLE 1

1O-2
0.0678
1o-2
0.0718
1o-2
0.4400
10-Z
0.1249
1o-2
0.0411
10-2
0.0534
1O-2
0.1130
10-2
0.0898
10-3

1o-2
0.0438
1O-2
a

0.2549
10-2
a

(K-)

0V2

Nagata et al. (1976)

Nagata et al. (1976)

Nagata et al. (1976)

Nagata et al. (1976)

Nagata et al. (1975)

Nagata et al. (1975)

Nagata et al. (1975)

Nagata et al. (1975)

Nagata and Yamada

(1973)

Nagata and Yamada

(1973)

References

25-60

13. Ethanol(l)toluene(2)
14.2-Propanol(l)n-heptane(2)
15. n-Pentanol(l)n-hexane(2)
16. n-Pentanol(l)2,3-dimethyIbutane(2)
17. n-Pentanol(l)2_methylpentane(2)
18. IsopentanoI(l)n-hexane(2)
19. n-Pentanol(l)3-methylpentane(2)

20. n-Pentanol(l)2,2_dimethylbutane(2)
21. Acetonitrile(l)benzene(2)
22. Benzene(l)n-heptane(2)
23. Acetonitrile(l)n-heptane(2)

25-55

12. Methyl acetate(l)ethanol(2)

45

25-50

45-70

25

25

25

25

25

25-45

30-60

25-45

11. Methyl acetate(l)methanol(2)

463.88
0.69
493.99
0.27
26.36
- 1.28
478.63
-1.46
1459.60
- 5.97
1829.80
- 8.35
1466.90
-1.40
1727.10
-0.85
1741.60
- 0.02
1369.50
1.65
1447.90
2.88
1801.30
- 0.36
1760.50
- 0.72
229.62
1.18
- 172.11
-4.58
1233.60
- 17.63

444.03
- 2.94
488.52
- 2.91
767.46
- 2.08
577.71
- 3.25
591.59
0.09
864.35
- 0.69
319.91
- 1.39
544.81
1.65
529.40
1.57
184.05
- 1.97
85.29
- 2.74
636.60
1.80
557.93
1.65
487.52
- 2.88
771.67
3.81
979.36
10.81

0.5928
0.3566
0.6556
0.2030
0.1516
- 0.4945
0.5723
0.4540
0.4808
0.2046
0.4874
0.9453
0.4592
0.8791
0.5589
0.1410
0.5448
0.1297
0.3390
- 0.1072
0.3182
- 0.1198
0.5565
0.1459
0.5522
0.1362
0.6402
- 0.1085
0.3639
-0.1181
0.2358
- 0.2596
10-s
0.0878
10-4
0.1583
10-3
0.0316
10-s
0.0875
1o-2
0.1068 d
1o-2
0.1737
10-2
0.1678
1o-2
0.0991 d
10-2
0.0806
10-2
0.0873
10-l
0.1612
10-r
0.1805
10-2

1o-3
0.2000
;0-3

0.0811
to-3

Nguyen and Ratcliff (1975a)

Sayegh and Ratcliff (1976)
Palmer and Smith (1972)
Monfort (1983)
Palmer and Smith (1972)
Lundberg (1964)
Palmer and Smith (1972)

Nguyen and Ratcliff (1975a)

Sayegh and Ratcliff (1976)
Nguyen and Ratcliff (1975a)
Sayegh and Ratcliff (1976)
Nguyen and Ratcliff (1975a)
Sayegh and Ratcliff (1976)
Nguyen and Ratcliff (1975a)
Sayegh and Ratcliff (1976)
Nguyen and Ratcliff (1975a)
Sayegh and Ratcliff (1976)

Van Ness et al. (1967)

Van Ness et al. (1967)

Nagata et al. (1972)

Nagata et al. (1972)

40

28.1,4-Dioxane(l)acetonitrile(2)
29. Carbon tetrachloride(l)diethyl sulfide(2)
30. Chloroform(l)diethyl sulfide(2)
31. Toluene(l)1-chlorohexane(2)
32.1~Chlorohexane(l)ethylbenzene(2)
15-70

15-70

25

25

15-59

15-90

5-85

5-65

=ti, - =k,
(C)

27. n-Butanol(l)n-hexane(2)

24. Ethanol(l)cyclohexane(2)
25. Water(l)butyl glycol(2)
26. n-Butanol(l)n-heptane(2)

System

TABLE 1 (continued)

c4

335.69
-0.14
605.00
1.55
302.15
0.05
635.70
0.92
- 11.61
6.35
33.45
- 4.98
156.20
1.80
66.18
0.03

787.47
- 2.56
1536.00
0.53
739.85
1.23
- 151.06
0.10
- 148.28
0.11
- 576.05
7.68
- 213.03
0.27
- 112.53
0.53

( ca 1 mol-
956.01
- 0.50
654.50
1.81
487.05
- 1.99

K-l)

c3
(cal mol- )

1772.50
- 1.19
802.63
3.73
1147.10
- 1.67

(calmol-

c2

cl
(Cal mol-)
K-l)
(K-l)
0.0812 d
1o-3
0.428
1O-2
0.2441
1O-2

1o-3
0.0808
1o-3
c
1o-3
0.2173
1O-3
0.2978
10-l
0.1395
1O-3
0.1405
10-r
0.1957
10 -

0.4546
0.5746
0.1000
0.4269
0.4339
-0.2605
0.5225
0.2110
0.5381
0.8901
0.5131
0.3400
0.6960
0.8171
0.4380
0.5900
0.1570
-0.5564
0.1890
0.2100
0.6499
0.2936

er/r

g-l)

c5

Paul et al. (1988)

Francesconi
and Commelh (1988)
Gray et al. (1988a)
Gray et al. (1988b)
Gray et al. (1988a)
Gray et al. (1988b)
Paul et al. (1988)

Nguyen and Ratcliff (1975b)

Berro et al. (1982)

Scatchard and
Satkiewitcz (1964)
Scatchard and
Wilson (1964)
Savini et al. (1965);
Berro and Peneloux (1984)
Nguyen and Ratcliff (1975b)

References

a
b

d
i

Parameters
Parameters
Parameters
Parameters
Parameters
Parameters

obtained by
obtained by
obtained by
which show
which show
obtained by

33. l-Chlorohexane(l)n-propylbenzene(2)
34. 1,3-Dioxolane(l)methylcyclohexane
35.1-Chloropentane(l)di-n-butyl ether(2)
36. 1,2-Dichloroethane(l)di-n-butyl ether(2)
37. l,l,l-Trichlorethane(l)di-n-butyl ether(2)
38. Ethanol(l)acetone(2)
39. Acetone(l)water(2)
40. Cyclohexane(l)methyl methactylate(2)
41. Isobutyric acid(l)cyclohexane(2)
42. Trimethylacetic acid(l)cyclohexane(2)
43. Isobutyric acid(l)n-heptane(2)
44. Trimethylacetic acid(l)n-heptane(2)
- 87.55
0.95
878.00
- 0.54
- 22.39
- 1.34
- 118.84
- 1.11
464.84
2.31
260.36
- 4.07
653.56
9.27
227.63
- 1.83
914.38
2.76
566.26
1.31
1109.80
3.34
558.93
1.19
40.77
1034.30
- 0.84
69.18
1.52
576.79
0.22
- 496.65
- 1.59
398.08
1.61
657.75
- 1.71
600.09
- 1.48
417.11
0.51
255.71
1.11
508.12
0.83
277.79
1.24

- 0.56

0.1000
- 0.9886
0.5912
0.5490
0.1001
0.3295
0.6496
0.6090
0.1072
0.9571
0.4199
- 0.2058
0.6725
- 0.8256
0.4454
- 0.8637
0.5590
0.1042
0.4235
0.1868
0.6758
0.9379
0.3111
0.2009

0.4325
10-z
0.0915
10-z
0.2266
10-2
0.1893
10-s
0.2507
10-s
0.0454
10-2
0.1495
10-s
0.0358
10-s
0.0661
10-a
0.0868
10-2
0.0252
10-s
0.0370
10-2

Nagata and Yamada (1973) by using hE data and isothermal VLE data.
Nagata et al. (1972) by using hE data and isothermal VLE data.
Berro et al. (1982) by using hE data and isothermal VLE data.
partial miscibility.
complete miscibility.
Berro and Peneloux (1984) by using hE data and isothermal VLE data.

25-45

25-45

25-45

25-45

25-75

50-200

25-150

10-70

5-77

5-50

40

25-90

Lark et al. (1987)

Lark et al. (1987)

Lark et al. (1987)

Nicolaides and Eckert (1978)

Campbell et al. (1987)
Villamanan and Van Ness (1984)
Griswold and Wong (1949)
Luo et al. (1987)
Hull and Lu (1984)
Lark et al. (1987)

Paul et al. (1988)

Paul et al. (1986)

Paul et al. (1986)

Castellari et al. (1988)

Paul et al. (1988)

120
TABLE 2
Temperature-dependent

parameters

System

of the UNIQUAC

Twin-Max
(C)

25. Water(l)butyl gfycol(2)

26. n-Butanol(l)n-heptane(2)
27. n-Butanol(l)n-hexane(2)
28. 1,4-Dioxane(l)acetonitrile(2)
29. Carbon tetrachloride(l)diethyl sulfide(2)
30. Chloroform(l)diethyl sulfide(2)
31. Toluene(l)1 -chlorohexane( 2)
32. l-Chlorohexane(l)ethylbenzene( 2)
33. l-Chlorohexane(l)n-propylbenzene(2)
34. 1,3-Dioxalane(l)methylcyclohexane(2)
35. l-Chloropentane(l)di-n-butyl ether(2)
36. 1,2-Dichloroethane(l)di-n-butyl ether(2)
37. l,l,l-Trichloroethane(l)di-n-butyl ether(2)
38. Ethanol(l)acetone(2)
39. Acetone(l)water(2)
40. Cyclohexane(l)methyl methacrylate(2)
41. Isobutyric acid(l)cyclohexane(2)
42. Trimethylacetic
acid(l)cyclohexane(2)
43. Isobutyric acid(l)n-heptane(2)
44. Trimethylacetic
acid(l)n-heptane(2)

5-85
15-90
15-59
40
25
25
15-70
15-70
25-90
40
5-50
5-77
10-70
25-150
50-200
25-75
25-45
25-45
25-45
25-45

model and the variation

do
(K)
d,
(K2)

d,
(K)
d,
(K)

377.68
- 49434.0
- 940.63
767180.0
1196.8
2048.2
- 358.85
50510.0
-614.33
167990.0
737.21
- 204310.0
38.61
19241.0
- 155.44
21241.0
- 32.27
- 2524.3
240.83
771.0
56.77
652.8
33.91
- 7744.9
- 102.18
- 2312.1
156.34
69392.0
712.49
- 228200.0
- 64.94
15894.0
429.29
- 75521.0
316.51
- 54611.0
682.23
- 105450.0
184.01
- 24171.0

426.31
- 89183.0
- 389.75
62225.0
- 347.83
52997.0
781.02
- 106120.0
770.32
- 219510.0
- 487.55
109680.0
- 58.47
- 12424.0
173.15
- 26767.0
29.03
995.45
- 175.56
53095.0
-41.30
- 1115.6
- 19.95
4126.3
107.72
8799.0
- 277.82
52280.0
- 461.03
252910.0
6.36
24213.0
- 161.10
42030.0
- 126.18
29692.0
- 284.38
50801.0
- 18.96
5405.33

of the fit
et/2

0.2017
0.2651
0.0943
0.2748
0.2668
0.1098
0.1592
0.2105
0.3107
0.1485
0.3055
0.3046
0.2368
0.1053
0.1638
0.0439
0.0620
0.0817
0.0666
0.0572

121

The NRTL model gives multiple roots for the systems 1, 2, 11, 12 and 19,
as may be seen from Table 1. The NRTL parameters
for the systems
n-pentanol-2-methyl
pentane and ethanol-cyclohexane
predict partial miscibility, which is not, however, predicted by the UNIQUAC
model. Also,
although the system water-butyl
glycol shows phase splitting, the NRTL
parameters
predict complete miscibility, whereas the UNIQUAC
model
predicts partial miscibility. Multiple roots also result when the UNIQUAC
model is used. The parameters that yield the best variation of the fit have
been tabulated. For the system acetonitrile-n-heptane,
which shows phase
splitting, the parameters of both equations predict partial miscibility. Tassios (1976) claims that by changing the initial values of parameters it may be
possible to obtain the correct values for some systems, as is seen for the
system n-pentanol-3-methylpentane,
which is a highly non-ideal mixture.
Simultaneous predictions of vapor-phase composition,
P, gE and hE, by
the models are shown in Table 3. The volume and surface area parameters of
the UNIQUAC
model are given in Table 4. The average absolute error, S,
for gE, P and hE were calculated using

The root mean square deviation (RMSD) in predicting

compositions was calculated from the following equation

the vapor

phase

The values of S( gE), S(P) and RMSD were calculated at each isotherm for
gE. Pure-component
vapor pressures were obtained from the Antoine equation and the necessary parameters were taken from Reid et al. (1977). The
value of S( hE) was calculated at each isotherm for the hE data. The results
indicate the sensitivity of the NRTL and UNIQUAC
equations in representing gE, VLE and hE data simultaneously
at various isotherms, and also
show that the models are system-dependent.
For a total of 947 data points
for gE, the average absolute errors for gE and p calculations
from the
NRTL model are 7.4% and 3.3%, respectively,
while the corresponding
values from the UNIQUAC model are 7.2% and 2.9%. The values of RMSD
for the NRTL and UNIQUAC models are 1.9% and 1.6%, respectively. For

10
10
11

55
55
55

45

45

50

45

Ethyl formate(l)methanol(2)

Ethyl formate(l)ethanol(2)

Ethyl formate(l)1-propanol(2)

Ethyl formate(l)2-propanol(2)
11

12

12

11

55

Methyl acetate(l)cyclohexane(2)

Methanol(l)ethyl acetate(2)
Ethanol(l)ethyl acetate(2)
2-Propanol(l)ethyl acetate(2)
l-Propanol(l)ethyl acetate(2)

12
9
11
8
9

30
40
50
35
40

((3

T(gE>

Methyl acetate(l)benzene(2)

System

and UNIQUAC

25
35
45
25
35
25
35
25
35
25
35
45
25
35
45
25
35
45
25
35
45
25
35
45

25
35

(Cl

T(hE)

11
11
9
12
12
12
16
13
18
11
20
9
8
11
9
6
13
9
8
13
9
13
12
11

13
12

4.71

5.16

2.17

1.48

6.62

22.75

3.07

1.22

19.88
13.01
11.36
0.70
3.28

S(gE)

NRTL

0.59
0.46
1.16
4.07
4.10
1.75
3.10
3.79
4.70
3.15
3.42
1.86
1.85
3.14
1.46
2.93
3.54
1.68
0.845
2.36
2.66
1.04
1.29
1.75

2.96
8.73

S(hE)

1.83

1.59

4.64

1.08

1.33

6.21

1.34

1.56

0.34
1.06
0.41
2.50
2.25

S(P)

- _.

2.67

2.41

6.06

0.70

0.62

5.14

3.96

1.28

0.76
0.38
0.58
2.10
2.71

_.

4.48

5.26

2.58

1.68

6.63

22.76

2.61

1.23

20.05
11.66
14.50
1.98
3.21

S(gE)

._ - ..-

4.75
3.82
4.36
4.53
5.22
4.06
4.04
3.25
4.59
3.36
2.13
2.42
10.42
4.71
7.82
10.54
4.59
7.85
10.04
3.10
8.35
8.09
1.43
8.46

5.22
6.58

S(hE)

UNIQUAC

15.83

1.39

4.79

1.15

1.35

6.23

1.32

1.52

0.37
1.13
0.48
2.01
1.88

S(P)

8.43

1.00

0.31

0.48

0.98

23.43

0.90

0.48

0.71
0.40
0.51
2.31
2.86

RMSD

models using the temperature-dependent

RMSD

Average absolute error, S x 100 and RMSD x 100

Simultaneous representation of hE and isothermal VLE data by the NRTL

parameters

TABLE 3

9
9
9
9
9
19
11

25
25
25
25
45
70
45

n-Pentanol(l)2,3-dimethylbutane(2)
n-Pentanol(l)2_methylpentane(2)
Isopentanol(l)n-hexane(2)
n-Pentanol(l)3_methylpentane(2)
n-Pentanol(l)2,2dimethylbutane(2)
Acetonitrile(l)benzene(2)
Benzene(l)n-heptane(2)

n-Pentanol(l)n-hexane(2)

2-Propanol(l)n-heptane(2)

30
45
60
30
45
60
25
30
45
25

Ethanol(l)toluene(2)
18
18
17
17
17
16
9

10
13

45
55

Methyl acetate(l)ethanol(2)

13
13

35
45

Methyl acetate(l)methanol(2)

2.75

13
14
8
4

45
25
50

1.48
1.18
1.01
2.57
2.25
1.87
2.26

7.60
3.79
9.19

2.81

0.35
0.22
2.38

0.83
1.03
0.72
0.36
1.05
1.97
1.22

0.07

2.85

0.13

0.04

7.72

2.54

7.12

2.63

3.24

7.21

3.42

0.03

0.09

2.52

2.75

1.34
0.87
0.69
2.18
1.46
1.05
0.03

1.17
1.44

2.63
3.04
1.67
1.08
0.70
2.29
1.30
0.76
2.06

0.38
0.68

0.75
1.17

3.58

1.54
0.93
1.92
3.80
3.71
3.41
9.06
5.91
5.05
14.67
11.65
10.63
15.30
15.59
15.66
2.76

3.16

8.78
12.88

4.89
4.15

14
16
10
11
12
7
26
23
26
24
22
21
9

45

25

25

25

25

25

25
35
45
25
35
45
25
45
60
30
45
60
25

7.65
4.26
8.70

2.55

2.58

3.24

2.51

2.69

1.97
2.41
2.78
3.23
3.16
2.95
2.14

9.13
12.90

4.94
4.07

2.72
3.08
2.55
2.64
0.71
1.04
0.61

4.67
5.18
4.89
4.02
2.11
1.40
1.60
1.30

2.31

4.21

2.79
3.02
1.32
1.27
1.33
3.89
2.98
2.22
5.52

0.77
1.14

3.58
1.25
4.02
6.54
2.55
6.26
10.43
6.20
8.20
11.95
9.14
13.86
3.30

1.31
0.78
0.49

0.05

0.11

0.19

0.11

0.08

0.91
0.78
0.80
2.30
2.11
2.08
0.20

1.17
1.37

0.41
0.71

n-Butanol(l)n-hexane(2)
l+Dioxane(l)acetonitrile(2)
Carbon tetrachIoride(l)diethyl sulfide
ChIoroform(l)diethyl sulfide(2)
Toluene(l)1-chIorohexane(2)

n-Butanol(l)n-heptane(2)

Water(l)butyl gIycol(2)

Acetonitrile(l)n-heptane(2)
Ethanol(l)cycIohexane(2)

System

TABLE 3 (continued)

5
20
35
50
65
5
25
45
65
85
30
45
55
55
15
40

9
9
9
9
9
8
8
8
8
8
19
22

23
12
10
9
12
12

5
20
35
50
65
5
25
45
65
85
60
90

59
40
25
25
50
70

15
25

25

25

45

T (hE)
(C)

45

VgE)
(C)

15.68
5.92

11
10

8.00
5.84

9.60

10

19
17

1.97

1.71
1.54
2.02
1.66
1.81
26.46
26.46
25.98
22.42
22.38
6.47
3.59

7.09

S(gE)

NRTL

10
10
10
10
10
8
8
8
8
8
17
17
10
10
10

13

Average absolute error, S

4.31
7.43

2.86

3.56

6.90

9.53
3.90
3.82
4.60
4.94
31.42
17.11
21.78
37.83
30.52
14.89
14.48
22.58
8.58
4.13

2.68

0.23
0.35

1.26

0.50

1.32

2.90

1.60
2.56
2.45
2.24
2.70
15.44
14.48
14.95
15.34
13.73
2.05
1.44

11.65

S(P)

100 and RMSD

S(hE)

100

0.22
0.26

0.75

0.76

1.28

0.77

0.98
1.36
1.60
1.81
1.83
0.94
1.88
2.08
2.61
2.00
0.82
0.92

8.73

RMSD

9.75
12.31

5.93

15.46

12.68

3.40

5.35
4.35
3.84
4.03
4.74
9.50
8.90
8.88
8.54
8.65
4.47
2.14

7.31

1.85
2.26

2.90

5.60

12.30

12.73
7.65
7.32
7.77
2.11
11.95
13.00
13.16
10.62
12.87
18.60
22.00
18.00
23.00
5.10

2128

S(hE)

UNIQUAC
S(gE)

0.22
0.22

1.27

0.49

1.74

2.76

2.50
1.73
1.52
1.67
1.87
7.53
6.29
6.75
6.31
6.88
0.51
0.92

12.34

S(P)

0.19
0.09

0.75

0.55

1.64

0.56

0.98
1.03
0.92
1.04
1.30
0.55
0.39
0.49
0.70
1.04
0.83
0.83

9.22

RMSD

Isobutyric acid(l)cyclohexane(2)
Trimethylacetic acid(l)cyclohexane(2)
Isobutyric acid(l)n-heptane(2)
Trimethylacetic acid(l)n-heptane(2)

Cyclohexane(l)methyl methacrylate(2)

Acetone(l)water(2)

Ethanol(l)acetone(2)

l,l,l-Trichloroethane(l)di-n-butyl ether(2)

1,2-Dichloroethane(l)di-n-butyl ether(2)

l-Chlorohexane(l)ethylbenzene(2)
l-Chlorohexane(l)n-propylbenzene(2)
1,3-Dioxalane(l)methylcyclohexane
l-Chloropentane(l)di-n-butyl ether( 2)
12
12

40
50

100
125
150
100
150
200
45
60
75
25
45
25
45
25
45
25
45
9
11
10
14
14
14
17
17
16
12
11
11
12
12
12
10
10

13
12
13
12
13

26

40

57
77
97
50
70

10
14
8

50
70
90

9
9
9
8

35
35
35

11

19

11
12
11
12
12

20
19
19
19
19

17
19
19
19
16

35

25

50

25
10
35
25
50

5
25
40
5
25

15
25
25
15
40

3.00
3.06
1.51
11.27
11.02
5.95
2.32
2.55
2.55
1.74
1.50
5.95
5.22
0.83
0.80
2.36
2.75

14.84
10.11
14.05
24.05
12.15

18.09
12.84

6.39

16.53
9.30
17.31

0.29

1.16

0.76

3.32

0.38

1.77

2.95
3.00
1.13
1.97
1.76

9.49
3.81
4.01
4.30
2.11

7.67
10.14
3.11
4.13
2.00

1.01
1.42
2.98
3.62
3.27
4.14
0.26
0.24
0.46
2.88
2.34
4.38
3.60
1.47
1.44
3.86
3.72

0.75
0.36
0.31
0.43
1.08

19.59
18.69

3.99

0.25
0.25
0.41

1.77
1.17
0.83
2.50
3.43
3.69
0.51
0.50
0.45
3.96
4.66
0.98
2.51
4.90
4.85
1.63
2.28

0.46
0.19
0.25
0.08
0.32

3.66
2.82

4.79

0.20
0.18
0.50

2.41
4.72
5.14
8.00
8.80
5.79
3.39
2.55
2.75
2.93
3.25
5.64
4.45
5.00
4.36
3.28
3.89

16.39
9.21
15.05
20.44
19.93

17.39
15.02

10.93

22.12
12.04
18.10

1.97

1.70

2.42

2.58

1.70

8.90

12.89
8.31
12.71
7.80
7.80

17.80
10.46
30.33
5.71
4.36

3.77
5.18
3.75
4.93
2.20

0.60
1.32
3.29
5.03
3.22
3.22
0.34
0.26
0.24
3.53
3.01
4.35
2.96
4.45
3.37
4.36
4.54

0.80
0.26
0.47
0.74
1.26

19.65
18.72

2.38

0.33
0.09
0.38

1.49
1.08
0.95
3.32
3.05
2.99
0.44
0.48
0.49
3.98
4.71
0.61
2.16
4.98
4.99
1.40
2.35

0.43
0.17
0.25
0.14
0.34

3.67
2.82

3.34

0.17
0.12
0.48

126
TABLE 4
Volume and surface area parameters

Methyl acetate
Benzene
Cyclohexane
Methanol
Ethyl acetate
Ethanol
2-Propanol
1-Propanol
Ethyl formate
Toluene
n-Heptane
n-Pentanol
n-Hexane
2,3-Dimethylbutane
2-Methylpentane
Isopentanol
3-Methylpentane
2,ZMethylpentane
Acetonitrile
Water
Butyl glycol
n-Butanol
l+Dioxane
Carbon tetrachloride
Diethyl sulfide
Chloroform
I-Chlorohexane
Ethylbenzene
n-Propylbenzene
1,3-Dioxolane
Methylcyclohexane
I-Chloropentane
Di-n-butyl ether
1,2-Dichloroethane
l,l,l-Trichloroethane
Acetone
Methyl methacrylate
Isobutyric acid
Trimethylacetic
acid

for the UNIQUAC

model

2.800
3.190
3.970
1.430
3.480
2.110
3.249
3.249
2.817
3.920
5.170
4.597
4.500
4.500
4.499
5.923
4.499
4.498
1.870
0.920
4.697
3.450
3.185
3.330
3.902
2.700
5.064
4.600
5.272
2.511
4.640
4.390
6.093
2.880
3.541
2.570
3.922
3.550
4.224

2.580
2.400
3.010
1.430
3.120
1.970
3.124
3.128
2.576
2.970
4.400
4.208
3.860
3.860
3.396
4.516
3.396
3.932
1.724
1.400
4.556
3.050
2.917
2.620
3.296
2.340
4.272
3.510
4.048
2.100
3.550
3.732
5.176
2.520
3.032
2.340
3.564
3.148
3.768

2.580
2.400
3.010
0.960
3.120
0.920
0.890
0.890
2.576
2.970
4.400
1.150
3.860
3.860
3.396
1.150
3.396
3.932
1.724
1.000
4.556
0.880
2.917
2.620
3.296
2.340
4.272
3.510
4.048
2.100
3.550
3.132
5.176
2.520
3.032
2.340
3.564
3.148
3.768

a total of 1101 data points for hE, the average absolute errors for hE
calculations from the NRTL and UNIQUAC models are 5.8% and 6.7%,
respectively. The predictions of the UNIQUAC model compare well with

127

those of the NRTL model, although the latter has six estimated parameters,
and the effect of temperature on g E, VLE and hE data is well represented
by both models. This shows that eqns. (2)-(4), (6) and (7) are capable of
expressing the temperature dependency of the models for various types of
mixture, including ones with hydrogen bonding.
Using the error matrix, the off-diagonal elements of the correlation
coefficient matrix, which is explained elsewhere in detail (Demirel and
Gecegormez, 1989), is calculated as
pjj =

Uij/(

p;;
=

I)
J

uiiujj)12

Pij

Pji

(17)

TABLE 5
The elements of correlation coefficient matrix, v: p,, = 1; pi, = p,,
P IJ

System a
2

27

22

38

43

25

0.461
0.354
0.645
0.707
0.087
0.482
0.777
0.671
0.794
0.723
0.596
0.330
0.456
0.476
0.722

0.271
0.203
0.789
0.230
0.566
0.326
0.247
0.624
0.838
0.119
0.348
0.293
0.328
0.736
0.428

0.304
0.262
0.236
0.274
0.041
0.938
0.168
0.303
0.894
0.842
0.530
0.042
0.800
0.859
0.864

0.744
0.946
0.535
0.758
0.970
0.531
0.336
0.419
0.153
0.530
0.693
0.922
0.530
0.820
0.357

0.348
0.335
0.016
0.568
0.937
0.100
0.573
0.167
0.499
0.464
0.568
0.029
0.306
0.306
0.909

0.942
0.579
0.611
0.414
0.546
0.862
0.580
0.616
0.938
0.796
0.232
0.034
0.420
0.717
0.457

0.778
0.589
0.951
0.904
0.598
0.449
0.001
0.014
0.002
0.027
0.459
0.893
0.987
0.312
0.007

0.923
0.899
0.718
0.935
0.811
0.979

0.892
0.137
0.424
0.096
0.427
0.985

0.976
0.993
0.944
0.997
0.987
0.984

0.960
0.969
0.873
0.923
0.937
0.986

0.999
0.985
0.989
0.974
0.983
0.995

0.982
0.990
0.988
0.991
0.989
0.983

NRTL
CL21
P31
p32
P41
IL42
P43
P51
p52
t453
CL54

P61
CL62
IL63
p64
p65

UNIQUAC
PZI
P31
p32
1141
p42
IL43

0.273
0.356
0.935
0.829
0.355
0.315

a 2, methyl acetate-cyclohexane; 3, methanol-ethyl acetate; 27, n-butanol-n-heptane; 22,

benzene-n-heptane; 38, ethanol-toluene; 43, isobutyric acid-n-heptane; 25, water-butyl
gIyco1.

0.887
0.956
0.612
0.998
0.846
0.931
0.999

c3

0.833
0.900
0.985
0.983
0.819
0.972
0.999

c4

CS

0.964
0.961
0.977
0.841
0.958
0.955
0.055

0.729
0.977
0.983
0.988
0.951
0.950
0.999

acetate; 27, n-butanol-n-heptane;

0.902
0.981
0.984
0.997
0.953
0.971
0.997

0.916
0.947
0.954
0.999
0.966
0.999
0.954

d,

22, benzene-n-heptane;

0.793
0.969
0.947
0.999
0.967
0.999
0.947

d,

C2

Cl

0.842
0.838
0.913
0.991
0.855
0.957
0.997

UNIQUAC

NRTL

P:

a 2, methyl acetate-cyclohexane; 3, methanol-ethyl

isobutyric acid-n-heptane; 25, water-butyl glycol.

2
3
27
22
38
43
25

System

The global correlation coefficients

TABLE 6

0.786
0.983
0.988
0.999
0.974
0.999
0.988

d4

38, ethanol-toluene;

0.916
0.983
0.985
0.999
0.963
0.999
0.985

d3

43,

129

where uii represents the elements of the error matrix. If v is positive definite,
p < 1 for all elements. If p = 0, then the parameters are uncorrelated and if
p = 1, the par ameters are completely correlated. For a given parameter, the
global correlation coefficient is given by

/.A;= 1 -

[ UkkVLk]

-l

(18)

and is the correlation between it and that linear combination of the other
parameters most highly correlated with it. All such coefficients should be
between zero and one for a positive definite error matrix. The values of error
matrix correlations and the global correlation coefficients for some of the
systems are given in Tables 5 and 6, respectively. The parameters for some
of the systems are highly correlated, but for such parameters it is not
possible to specify unique values from a given set of data. Such problems
have arisen when the same free energy function is used for two of the
phases, as in LLE, at points where the mole fractions in two phases are
identical.

CONCLUSIONS

Although the simultaneous fit of Gibbs energy and enthalpy of mixing

data for 44 binary systems is satisfactory with the NRTL and UNIQUAC
models, choice of the best model is mainly system-dependent. The use of
temperature-dependent
parameters improves the performance of the models,
but care should be exercised in the selection of the best model for a given
system, and in the estimation of the parameters for especially non-ideal
mixtures.

ACKNOWLEDGMENT

The authors thank the Computer Centre of Cukurova University for the
computation facilities provided.

LIST OF SYMBOLS

aij
Cl,

c3

c29 c4

UNIQUAC binary interaction parameter related to riT

values of (g2, - gir) and (g,, - g,,) at 0C (cal mol-)
coefficients of temperature change of (g,, - g,,) and (g,, - g,,)
(cal mol- K-)

130

value of (Y,~at 0 C
coefficient of temperature change of ai2 (K-l)
6
UNIQUAC parameters related to ajj (K)
d,, d,
UNIQUAC
parameters related to ajj (K)
6 d,
F
objective function as defined by eqn. (9)
excess molar Gibbs energy (cal mol-)
gE
constant in eqn. (5)
Gi
Gh
Gibbs energy of mixing (cal mol-)
G, G second and third derivative of Gibbs energy of mixing with respect
c5

excess enthalpy of mixing (cal mol-)

number of experimental
hE and gE data points, respectively, at a
specified isothermal temperature
number of isothermal system temperatures
for hE and gE data,
respectively
number of parameters
molecular geometric area parameter for component i
molecular interaction area parameter for component
i
total pressure (Pa)
molecular volume parameter for pure component
i
gas constant (cal mall K-)
root mean square deviation
absolute temperature (K)
average absolute error (eqns. (13), (14), (15))
elements of error matrix
liquid-phase mole fraction of component i
vapor-phase mole fraction of component
i

hE
m, n
M, iv
NP
4;
4,!
P
r,
R
RMSD
T
s
ij
xi
Yi

Greek letters
a12

;
u
7ij
7,;
pij
p,,

non-randomness
constant for binary l-2 interaction
activity coefficient of component i
area fraction of component
i in residual contribution
coefficient
variance of the fit
NRTL binary parameter
UNIQUAC binary parameter
elements of correlation coefficient matrix (eqn. (17))
elements of global correlation vector (eqn. (18))

Subscripts
exptl
calcd

experimental
calculated

to the activity

131

4 .i
max
min

component
maximum
minimum

Superscript

excess

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