Fluid Phase Equilibria 173 (2000) 5764

A simple modification of the NRTL equation

Alessandro Vetere
SNAMPROGETTI/RICE, Via Maritano, 26, 20097 San Donato Milanese, Italy
Received 15 February 2000; accepted 7 June 2000

Abstract
A simple modification of the NRTL equation is proposed which consists of inserting the ratio of the molar
volumes of the pure compounds as a multiplying factor of the binary parameters Gij and Gj i . The suitability of this
modification is evaluated by following two procedures in order to correlate or to predict the VLE of several binary
systems taken from the literature ranged according their non-ideality degree, namely
the prediction of the VLE data assuming the geometric mean gij = (gii gjj )0.5 for the energy interaction parameter
related to the ij interactions;
the correlation of the above data according to the NRTL equation written in the one-parameter form, as suggested
by Tassios.
The modified NRTL equation appears significantly more reliable than the NRTL in its classical form in both cases.
As a rule, the improvement is more relevant the higher is the non-ideality of the considered system. 2000 Elsevier
Science B.V. All rights reserved.
Keywords: NRTL; VLE; Correlation; Prediction

1. Introduction
Among the modern equations for the excess Gibbs energy of mixing, the NRTL equation exhibits some
outstanding features not shared by other similar relations. Of the greatest importance are the recognized
excellent balance between simplicity and reliability and the capability of dealing with any type of system.
The universality of the NRTL equation stems from the effort by Renon and Prausnitz [1] aimed at
overcoming the main limitation of the Wilson equation: the inability to predict the miscibility gap. Further,
the sound theoretical basis of the NRTL equation is confirmed by some works which exploit its intrinsic
predictive power. Vetere [24] showed that the VLE of binary systems can be predicted according to the
following simple procedure:

Fax: +39-2-520-56757.
E-mail address: silvvet@tin.it (A. Vetere).

0378-3812/00/$20.00 2000 Elsevier Science B.V. All rights reserved.

PII: S 0 3 7 8 - 3 8 1 2 ( 0 0 ) 0 0 4 0 0 - 3

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A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

1. The energy interaction parameters of pure compounds are calculated by using the Tassios method [5],
as
gii = (1Hv RT)

(1)

2. The sum of the exponent terms which appear in the expression of the binary NRTL parameters, Gij and
Gj i , can be related through simple relations to the pure component Hildebrand solubility parameters,
as
2gij gii gjj = A + B(i j )

(2)

the A and B constants being characteristic values of families of systems which disclose similar
chemico-physical properties.
3. The asymmetry of a system expressed by the ij / j i ratio obeys, in turn, a rule similar to Eq. (2), with
ij
= a + b(gii gjj )abs
(3)
ji
In summary, if the corpus of literature data is grouped in few families for both aqueous and non-aqueous
systems, the prediction of VLE reduces to the evaluation of the four constants in Eqs. (2)(3). These
values can be obtained by correlating the VLE data of some well-studied systems which can be
considered representative of a family of systems.
However, this bright scenario is shadowed by one drawback: the NRTL equation appears inferior to the
Wilson equation in treating the strongly asymmetric systems which disclose also strong deviations from
the ideal behavior. This inaccuracy is particularly evident in the range of very low molar concentrations.
The aim of this work is twofold: to clarify the reason for this behavior on the basis of the assumptions embodied in the NRTL equation and to propose a simple modification which amends the above
inconsistency.
2. The proposed model
A well-known empirical observation which can be drawn from VLE experimental data is the dependence
of the value of the limiting activity coefficient on the molar volume of solutes. This rule is enlightened
by the i values reported in Table 1 for several aqueous mixtures. As can be seen, the i of water is
always appreciably lower than the corresponding i value of the solvent when the latter is characterized
by a higher molecular volume. Although this rule is not without exceptions, it can be assumed as a point
of reference for our inquiry. Several theories of liquid solutions embody this condition. For example, in
the context of the Scatchard-Hildebrand equation we have
ln i Vi

(4)
i

is given by the Wilson equation:

A more complex relation for





gij gii
gij gjj
Vj
Vi

exp
exp
ln i = 1 ln
Vi
RT
Vj
RT

(5)

On the contrary, the corresponding relations for the NRTL equation, namely
ln i = ji + ij Gij

(6)

A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

59

Table 1
Limiting activity coefficients in aqueous mixtures [6]
Second compound

T ( C)

H2 O

Page no. of [6]

Acetic acid
Ethanol
2-Propanol
2-Butanone
Ethylacetate
n-Butanol
2-Methyl-1-propanol
Pyridine
Methyl-butylamine
Methylpyridine

100118
40
60
73.6
40
25
98
68
20
70

1.63
2.37
4.15
7.28
9.71
7.02
5.89
2.95
2.47
3.00

3.07
4.17
15.11
18.11
12.05
72.37
49.06
20.41
17.83
62.00

105
190
327
359
395
408
438
463
481
504

where
gij gjj
RT
gij gii
ji =
RT

ij =

(7)
(8)

and
Gij = exp(ij ij )

(9)

is clearly independent of the ratio of the molar volumes of pure compounds.

In the Wilson equation, the exponent term is tuned by the ratios Vi /Vj and Vj /Vi , which are absent in
the NRTL equation. If Vi < Vj , the above ratios dump the i value of the low molar volume compounds
(see Eq. (5)), thus enabling a better correlation of the VLE data when i  j . At first glance, it is
tempting to correct the NRTL equation as suggested by the Wilson model. Tentatively, by applying a very
rough rule, Eq. (6) must be rewritten as
ln i = ji +

Vi
ij Gij
Vj

(10)

However, there are more cogent reasons to assume Eq. (10) instead of Eq. (6): if we introduce the
volumetric molar fractions instead of the molar fractions in the context of the non-random two-liquid
theory, the local mole fractions must be rewritten as
xii = xi Vi exp(ij gii )

(11)

xij = xi Vi exp(ij gij )

(12)

xjj = xj Vj exp(ij gjj )

(13)

xji = xj Vj exp(ij gij )

(14)

By inserting these relations in Eq. (A5) of [6],

x1 x11
x1 x21
x2 x22
x12 x2
g11 +
g21 x1 g11 +
g22 +
g12 x2 g22
uE =
x11 + x21
x11 + x21
x12 + x22
x12 + x22

(15)

60

A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

we have in a few steps



ji (Vj /Vi )Gji
ij (Vi /Vj )Gij
uE
+
= xi xj
RT
xi + xj (Vj /Vi )Gji xj + xi (Vi /Vj )Gij

(16)

which justifies relation (10).

In summary, the modification proposed in this work saves the analytical form of the NRTL equation
provided that the following substitution is made:
G0ij =

Vi
Gij
Vj

(17)

G0ji =

Vj
Gji
Vi

(18)

and

Further, the use of the volumetric molar fractions directly follows from the Wilson theory of liquid
mixtures.
3. Applications
It is well known that both old and recent equations for calculating Ge are very efficient tools to
correlate the VLE equilibria of binary mixtures with two empirical constants, strongly associated or
reacting systems being the only exceptions. Therefore, it is mandatory to pose some constraints in order
to enlighten any difference between the old and the new analytical form of the NRTL equation regarding
their correlating or predicting power. In this work, two methods are applied. In both, the energy parameters
for the ii and jj pair interactions are evaluated by applying the Tassios method expressed by Eq. (1).
Further, in the first method, the cross parameter gij is calculated according to the relation
gij = (gii gjj )0.5

(19)

When the interaction energy parameters gii , gjj and gij are known, the NRTL binary constants Gij and
Gj i are defined through Eqs. (7)(9).
Admittedly, the geometric mean rule represents a very rough method to evaluate the properties of
a mixture from the pure component energy parameters only. However, it can be used with the aim of
disclosing the weak side of the examined equations.
The second method enables a more correct evaluation of the gij term by optimizing it from the correlation
of the experimental VLE data of each examined system.
A third constraint is represented by the choice of the binary mixtures processed in this work. Understandably, the mixtures which show low deviations from Raoults law are unable to disclose any appreciable
difference between the two equations. As a result, the choice was restricted to the systems characterized
by strong non-idealities, namely organic aqueous mixtures and mainly mixtures of non-polar compounds
in alcohols taken from two DECHEMA collections [7,8].
The examined systems are reported in Tables 24 along with the experimental range investigated and
the 1P% and 100 1y values for the two methods. In this work, the non-randomness parameter, ij , was
always put equal to 0.3. The volumetric data were calculated by applying the Rackett equation equipped

A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

61

Table 2
Comparison between the NRTL and the modified NRTL equations in correlating and predicting the VLE of some aqueous
mixtures
Second component

Experimental conditions

T ( C) P (mmHg)

Methanol
Dimethylamine
Ethanol
Acetaldehyde
1-4-Dioxane
1-Propanol
2-Propanol
Pyridine
Triethylamine
Dimethylisopro-pylamine

60
35
50
25
35
79.8
65.0
35.0
0.0
10.0

149538
42255
93202
206792
4282
352550
312397
3553
1720
1184

Mm =

Prediction (gij = (gii gjj )0.5 )

Correlation (Tassios method)

NRTL

NRTL

Modified NRTL

Modified NRTL

1P% 100 1y 1P% 100 1y

1P% 100 1y 1P% 100 1y

19.1
65.9
20.1
78.6
29.3
26.9
31.5
19.8
50.3
41.6

9.7
40.7
10.7
28.5
13.9
10.3
17.3
8.2
19.3
20.9

2.6
41.7
13.4
33.8
18.7
30.6
28.3
2.0
30.6
85.3

1.2
14.3
7.3
5.2
9.0
12.3
15.0
1.6
8.8
12.3

5.4
48.5
5.0
72.4
2.8
3.0
8.3
6.2
13.6
21.1

2.4
28.3
3.6
19.7
3.0
4.1
6.0
5.2
8.0
11.6

0.6
25.1
4.7
29.9
7.2
2.4
6.8
1.3
20.4
15.3

0.6
7.1
2.7
3.5
6.4
3.4
3.8
1.0
8.3
3.9

38.3

18.0

28.7

8.7

18.6

9.2

11.4

4.1

Table 3
Comparison between the NRTL and the modified NRTL equations in correlating and predicting the VLE of some polarpolar
mixtures
Mixtures

Experimental conditions Prediction (gij = (gii gjj )0.5 )

T ( C) P (mmHg)

Methanoldiisopropylether
Methanol1,2-dichloroethane
Propanolchlorobenzene
1,2-Dichloroethanepropanol
Chloroformethanol
Methanolethylacetate
Methylacetateethanol
Methylformatemethanol
Methanolnitromethane
Chloroformmethanol
Methanolacetonitrile
Methylformateethanol
Ethylformatemethanol
Ethanoldipropylether
MTBEmethanol
MethanolTAME
TAMEmethanol
EthanolMTBE
MTBEmethanol
1,1-Dichlorothaneformic acid
Mm =

5762
40
95
7892
60
7563
2333
25
6597
35
30
45
45
60
25
6584
6383
25
5264
30

730.0
150328
446693
700
377772
760
200
215585
760
230355
100114
247549
592609
278450
129266
760
760
129266
760
54125

NRTL

Correlation (Tassios method)

Modified NRTL NRTL

Modified NRTL

1P% 100 1y 1P% 100 1y

1P% 100 1y 1P% 100 1y

21.7
28.7
22.3
27.1
25.0
26.3
24.4
38.1
21.1
30.2
19.6
35.0
24.6
24.7
40.5
75.3
71.9
74.3
23.1
32.9

13.9
13.3
8.9
12.0
13.5
7.4
11.4
14.4
9.5
13.5
6.5
14.3
9.3
10.3
18.7
20.1
22.4
26.1
15.9
12.2

10.3
24.1
19.9
26.7
18.9
22.1
15.2
27.5
21.2
15.4
18.4
28.2
13.3
12.0
5.0
75.1
64.6
67.5
1.7
29.0

7.6
11.5
7.8
11.8
9.7
5.6
6.9
9.7
9.6
7.1
6.0
10.8
4.7
5.5
3.3
20.3
27.1
29.7
1.9
10.0

3.8
1.2
2.6
3.9
3.9
2.9
6.2
10.3
0.9
0.8
1.3
9.0
2.9
8.3
23.2
67.3
69.0
70.0
10.8
4.0

4.3
0.7
0.7
2.5
2.5
6.3
4.2
5.2
2.0
0.9
3.1
4.9
2.8
6.0
12.6
33.5
26.3
35.0
5.4
9.0

2.1
3.6
1.0
7.2
1.8
2.8
2.6
5.9
1.1
4.6
0.6
6.8
0.8
0.7
1.3
33.9
51.5
55.2
0.4
1.0

3.0
3.7
0.5
4.2
2.6
3.1
1.9
3.2
0.8
4.3
3.6
3.9
1.1
1.6
1.7
7.7
29.9
33.8
1.0
6.7

34.3

13.7

25.7

10.3

15.1

8.4

9.2

5.9

62

A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

Table 4
Comparison between the NRTL and the modified NRTL equations in correlating and predicting the VLE of some polarnon-polar
mixtures
Experimental conditions Prediction (gij = (gii gjj )0.5 )

Mixtures

T ( C)

Methylcyclopentaneethanol
Ethyliodureethanol
Carbon tetrachlorureethanol
Isopreneethanol
Hexaneethanol
Ethanolmethylcyclohexane
Ethanoltoluene
Ethanolbenzene
Methanolbenzene
1-Propanol-ethylbenzene
Ethanolbenzene
Benzene1-propanol
1-Propanolmethylcycloexane
Ethanolbenzene
Ethylacetateethanol
Isopreneethanol

6070
30
45
3060
35
35
55
45
55
97110
55
45
8793
60
70
3551

P (mmHg)

760
103201
193351
760
103301
120153
197308
271310
466678
760
359471
122238
760
377453
549712
760

Mm =

NRTL

Correlation (Tassios method)

Modified NRTL NRTL

Modified NRTL

1P% 100 1y 1P% 100 1y

1P% 100 1y 1P% 100 1y

32.0
46.0
36.7
44.3
42.6
42.6
30.7
35.6
35.2
24.2
35.8
43.6
34.6
31.1
16.4
50.7

17.8
22.9
17.4
28.3
19.6
22.4
14.8
16.6
17.5
9.6
17.9
15.6
18.2
16.6
7.2
16.8

24.2
40.0
29.1
26.7
28.2
31.7
25.8
28.9
29.0
21.2
29.3
39.4
25.4
25.3
9.1
23.5

12.9
18.9
13.0
13.7
10.6
15.3
11.9
12.9
15.0
8.3
13.8
13.5
12.8
13.4
3.7
4.6

17.5
17.4
10.7
31.1
22.0
13.3
2.1
5.4
5.3
4.1
5.7
12.3
10.3
4.8
2.6
31.1

8.7
9.0
5.3
19.1
9.9
6.0
1.2
4.3
2.0
1.3
3.4
6.3
6.7
4.5
2.4
9.2

0.3
7.7
1.6
5.8
2.9
3.9
4.1
1.4
7.9
0.9
2.0
8.7
2.3
1.1
0.6
3.4

1.2
5.3
1.8
3.3
2.2
3.9
3.3
1.7
7.8
1.0
2.2
5.2
1.7
1.7
0.7
0.8

36.4

17.5

27.3

12.1

12.2

6.2

3.4

2.7

with the critical constants reported by Reid et al. [9]. The vaporization enthalpies required by Eq. (1) were
taken from Reid et al. [10] or calculated through the Vetere equations which require Tb and M only [11].
Of course, the deviations of calculated values from the experimental ones pertaining to the first method
are relevant for both the new and the old version of the NRTL equation. However, the modified form
is significantly more reliable than the classical NRTL form for most of the examined systems (see the
overall mean values of AAD% in Tables 24). The same conclusions hold for the second method also. It
must be stressed that the latter gives acceptable results only in the case of the modified NRTL equation
(the only exception is represented by three systems linked to the MTBE and TAME synthesis for which
both equations give inaccurate values). This fact can hardly be overemphasized, since the gij values can
be accurately evaluated according to the Tassios method by using a limiting activity coefficient only.
The best data to be used are the independently measured infinite dilution activity coefficients, by some
methods as gas chromatography or differential ebulliometry [12,13].
The following points appear worthy of mention:
1. Several attempts to improve the performances of the modified NRTL equation by introducing an
exponent in the ratio of volumes, as (Vi /Vj ) or (Vj /Vi ) , were unsuccessful for any different from
unity.
2. An equal failure was encountered by applying the relation suggested by Schreiber and Eckert [14]:
2
gii = (1Hv RT)
Z
with various values of Z different from 2.

(20)

A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

63

Lastly, an example of the predictive power of the modified NRTL equation is given by the simple
relation
Vj
(21)
gij = 1233 333.3 (gii gij )0.5
Vi
with Vj > Vi , which enables the prediction with a good accuracy, according to the Tassios method, of
the VLE of the polarnon-polar systems (overall mean values: 1P % = 6.1 and 100 1y = 3.3). These
data are not reported in Table 4. The raison dtre of the modified NRTL equation is represented by the
above results.
List of symbols
A
constant of Eq. (2) (cal mol1 )
a
constant of Eq. (3)
B
constant of Eq. (2) (cal mol1 bar0.5 )
b
constant in Eq. (3) (mol cal1 )
e
excess Gibbs of mixing (cal mol1 )
G
Gij and Gj i binary constants of the NRTL equation
G0ij and G0ji binary constants of the modified NRTL equation
gij and gj i energy parameters for the pure component interactions (cal mol1 )
gij
energy parameters for the ij interactions (cal mol1 )
1Hv
vaporization enthalpy (cal mol1 )
M
molecular weight
overall mean value
Mm
1P%
average absolute percentage error of calculated pressures
R
universal gas constant (cal mol1 K1 )
T
absolute temperature (K)
normal boiling temperature (K)
Tb
E
u
excess enthalpy of mixing (cal mol1 )
Vi
liquid molar volume of compound i (cm3 mol1 )
molar fraction of compound i in the liquid phase
xi
xij
local molar fraction of compound i around the central molecule j
local molar fraction of compound j around the central molecule i
xj i
molar fraction of compound i in the vapor phase
yi
1yi
absolute mean deviation of calculated vapor phase compositions from the
experimental values
Z
co-ordination number
Greek letters
ij
non-randomness parameter of the NRTL equation

empirical constant

activity coefficient of compound i at infinite dilution

i
Hildebrand solubility parameter (cal0.5 mol1 cm1.5 )
ij
parameter of the NRTL equation defined by Eq. (7)
parameter of the NRTL equation defined by Eq. (8)
ji

64

A. Vetere / Fluid Phase Equilibria 173 (2000) 5764

Acknowledgements
The same idea as that reported in this work was also proposed independently by G. Soave, who, however,
refused a joint venture with myself.
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