Fluid Phase Equilibria 365 (2014) 123132

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Using the NRTL model with the Vidal equation of state EOS-qE
formulation for vapor/liquid equilibrium calculations
Mario R. Urdaneta P.
Laboratorio de Ingeniera Qumica Prof. Ydelfonso Arrieta, Escuela de Ingeniera Qumica, Facultad de Ingeniera, Universidad del Zulia (LUZ), Sector Grano
de Oro, 16th (Guajira) Avenue, Campus Dr. Antonio Borjas Romero, Building Petrleo y Qumica, Maracaibo, Venezuela

a r t i c l e

i n f o

Article history:
Received 6 February 2013
Received in revised form
26 December 2013
Accepted 1 January 2014
Available online 9 January 2014
Keywords:
Equation of state
Mixing rules
Vapor/liquid equilibrium

a b s t r a c t
In this work Vidal equation of state formulation (EOS-qE ) was evaluated for vapor/liquid equilibria (VLE)
isothermal calculations of binary and ternary mixtures, using NRTL model with 2 and 3 parameters for qE
representation in the low to high pressure range, resulting at least as convenient and accurate in application as the gamma/phi formulation and RedlichKister expansion; and better than using Huron/Vidal and
Wong/Sandler mixing rules EOS-GE formulation. Compared with referenced models, satisfactory predictions of VLE at temperatures different than that, at what correlation was obtained. Finally, isobaric VLE
was correlated in the experimental error precision range.
2014 Elsevier B.V. All rights reserved.

1. Introduction
VLE data is fundamental for separation process design, operation, evaluation and optimization. Obtaining VLE data using EOS
with PHIPHI scheme has been object of plenty of research work,
which has been reviewed by many authors like Valderrama, J.O.
[1]. A big portion of this research has been related with the composition dependence of the EOS parameters, for which no general
theory is known. Previously, Urdaneta, M.R., et al. [2] evaluated
successfully the EOS-qE Vidal, J. [3] modeling scheme using the
Redlich, O., et al. [4] expansion with 4-parameters (4PRK) and Wilson model for qE representation, for VLE isothermal calculations
of binary and ternary mixtures in the low to high pressure range
and isobaric VLE correlation. Following the same research strategy
and mathematical basement described in our previous article [2] in
this work was evaluated NRTL model [5] with 2 and 3 parameters
(2PNRTL and 3PNRTL) for qE representation of EOS-qE formulation, with results at least as convenient and accurate in application
as the gamma/phi formulation and better than using Huron/Vidal
(HV) [6] and Wong/Sandler (WS) [7] mixing rules EOS-GE formulation.

2. The Vidal EOS-qE formulation using the NRTL model

The following Eq. (1) gives the NRTL expression for qE in phase
Pi:
(qE )= z1 z2

  G
12 12
z2 + z1 G12

21 G21
z1 + z2 G21


(1)

where, zi = xi or yi ; 12 = g12 /RT ; 21 = g12 /RT ; G12 =

exp(12 12 ); G21 = exp(21 21 ) Using the generalized phase
superscript  (= v or l), q becomes:
q = z1 z2

  G
12 12

z2 + z1 G12


A =

(qE )
=
z1 z2

  G
12 12

21 G21
z1 + z2 G21

z2 + z1 G12

+ z1 q1 + z2 q2

21 G21
z1 + z2 G21

(2)


(3)


Here, any other solution model may be used for (qE ) , as

4-parameter RedlichKister expansion used by Urdaneta et al. [2]
resulting their expression: A = A0 + A1 (z1 z2 ) + A2 (z1 z2 )2 +
A3 (z1 z2 )3 .
Also,
 =

(z1 b1 + z2 b2 )P
RT

(4)

Eq. (5) may now be solved for Zl and Zv . The partial excess param
eters (q Ei ) of Eq. (6) and (7) are given by Van Ness and Abbott
[8]:
Tel.: +58 4246138450.
E-mail addresses: murdanetap@ng.luz.edu.ve, murdanetap@gmail.com
0378-3812/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.uid.2014.01.001

Z  + u1 Z  + u2 Z  + u3 = 0

(5)

124

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

32

parameter in cubic equation of state

n-hexane
equation-of-state parameter
equation-of-state parameter for pure species i
partial equation-of-state parameter parameter

excess equation-of-state parameter. q = (qE ) +

xq;
i i i
q Ei
partial excess equation-of-state parameter; Eqs. (6)
and (7)
u1 , u2 , u3 composite parameters for Peng/Robinson equation; Eq. (5)
xi
mole fraction of species i in liquid phase
mole fraction of species i in vapor phase
yi
generic mole fraction = xi or yi
zi
3PNRTL, 2PNRTL 3-parameter and 2-parameter NRTL equations, respectively
4PRK, 3PRK, 2PRK 4-parameter, 3-parameter and 2parameter Redlich/Kister equations, respectively
A0 , A1 , A2 , A3 parameters in the Redlich/Kister equation
carbon-dioxide
CO2
DEK
diethyl-ketone
GE
excess Gibbs energy
Methyl tert-butyl ether
MTBE
P
absolute pressure
saturation vapor pressure of species i
Pisat
R
universal gas constant
absolute temperature
T
gij
temperature independent constants of  ij parameters of NRTL local solution model
compressibility factor [Z = PV/(RT)]
Z
fi
fugacity of species i in solution
Greek letters
(or 12 ),  12 ,  21 parameters in NRTL equation

equation-of-state parameter
i
activity coefcient of species i in solution

denes a difference between a calculated and experimental property

i
fugacity coefcient for species i in solution


phase superscript meaning vapor ( = v) or liquid
( = l)

30
28
26

Pressure (bar)

b
nC6
q
qi
q i
qE

24
22

3PNRTL
3PRK
2PNRTL
WS-3PRK
Experimental Px1 Values

20
18
16

Experimental Py1 Values

14
0,0

0,2

0,4

0,6

0,8

1,0

Mole Fraction, x1, y1

Fig. 1. Experimental values [30] and correlated Pxy curves for ethanol(1)/H2 O(2) at
200 C using PRSV EOS with qE given by 3PRK, 3P and 2PNRTL, and WS-3PRK models
with parameters tted to Px data.

l and 
v , can now be calculated from Eq.
Fugacity coefcients 
i
i
(9):
 =
ln 
i

bi 
(Z 1) ln(Z   ) q 
I
i
b

(9)

where, I  = 1/ ln z  +  /z  +  and for PR EOS used

in this work, = 1 2 and  = 1 + 2. Eq. (9) leads through Eq.

(10) to values of P and vapor-phase mole fractions:
l = yi 
v (i = 1, 2, . . ., N)
xi 
i
i

(10)

Eq. (10) comes from VLE fundamental condition, fil = fiv and fi =
P
xi 
i

3. Correlation of data of binary systems

In the present work was used the same iterative algorithm outlined in Fig. 1 of our previous work [2] of VLE formulations for BUBL
P calculations, but adapted for 2 and 3 parameters NRTL model.
The initial guess values required for P and vapor composition may
be experimental. Alternatively, P may usually be taken as the xi weighted sum of the pure-species vapor pressures, with y1 from
Raoults law assumption.

Subscripts
i, j
identify a species

where:

u1 = 1 u2 = (q 3 2)

u3 = (1 + q )

2

As in our previous work [2], in this one it is used the PengRobinson EOS [9] improved by Stryjek and Vera [10]:

(q E1 )


(q E2 )


=

z22

z12

21


12

G21
z1 + z2 G21
G12
z2 + z1 G12

2
2

12 G12


(6)

(z2 + z1 G12 )2
21 G21
(z1 + z2 G21 )2


(7)

The Eq. (8) yields the partial parameters q 

:
i

Parameters for NRTL correlating equation for (qE ) were found

by a tting procedure based on Px1 data to minimize the sum
of squares of the pressure residuals, i.e., the differences between
experimental and calculated values of P. This is in direct analogy to
Barkers method [11] for the evaluation of parameters in expressions for GE . This procedure was applied with the 2PNRTL and
3PNRTL models, to t 34 binary Px1 data sets at 50 C [1220] for
rst 19 data sets (Group A) evaluated in our previous work [2] and
15 additional data sets (Group B) in the 4585 C range [11,2230]
evaluated in this work.
Results for the PR EOS pure and binary 4PRK parameters are
shown in Tables 1 and 2 for Group B data set. Table 1 presents
experimental vapor pressures, qi values, and bi values.
Table 2 gives values of the 4PRK parameters for the calculation of
l

= (q Ei ) + qi
q 
i

(8)

(qE ) , obtained by regression of the Px1 of Group B data sets (4PRK

parameters of Group A data appear in our previous work [2]) Also

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

125

Table 1
Pure-species properties at indicated temperature.
System

2-Butanone(1)/n-heptane(2) @ 45 C [27]
Benzene(1)/n-heptane(2) @ 80 C [11]
Methanol(1)/methylmethacrylate(2) @ 40 C [23]
Methanol(1)/methylmethacrylate(2) @ 50 C[23]
Chloroform(1)/1,4-dioxane(2) @ 50 C [25]
Pyridine(1)/tetrachloroethylene(2) @ 60 C [25]
n-Heptane(1)/2-pentanol(2) @ 75 C [29]
n-Heptane(1)/2-pentanol(2) @ 85 C [29]
n-Hexane(1)/dichloroethane(2) @ 50 C [21]
MTBE(1)/dichloromethane(2) @ 35 C [21]
Diethyl ketone(1)/n-hexane(2) @ 65 C [25]
Cyclohexane(1)/benzene(2) @ 40 C [24]
Ethanol(1)/n-hexane(2) @ 40 C [26]
MTBE(1)/chloroform(2) @ 40 C [28]
Methyl ethyl ketone(1)/toluene(2) @ 50 C [25]

P1 sat /kPa

P2 sat /kPa

q1

q2

b1

b2

29.099
101.008
35.498
55.697
68.200
14.839
48.320
67.370
54.040
49.624
29.000
24.600
17.980
59.847
36.090

15.344
57.077
10.099
15.899
15.600
12.810
16.490
26.310
31.140
85.265
90.200
24.400
37.290
48.463
12.300

14.1177
12.2245
15.0250
14.2597
13.0823
15.7187
12.5643
11.9986
12.4834
12.8485
13.9575
14.2997
15.7558
12.5309
13.7713

14.5119
12.2812
15.7062
14.9389
15.5284
15.5610
14.9528
14.1506
14.4075
12.8694
11.6132
14.6227
13.1127
13.6547
15.5145

83.3930
74.2916
40.9541
40.9541
63.4115
71.1849
127.5245
127.5245
110.5493
94.2929
97.0531
87.9167
54.0673
94.2929
82.4746

127.5245
127.5245
98.9217
98.9217
72.9034
89.9583
101.9836
101.9836
67.5713
54.2615
110.5493
74.2916
110.5493
63.4115
93.1746

A0

A1

A2

A3

RMS P/kPa

MRL

2.55724
0.96441
3.10694
3.03968
1.90745
1.43313
2.58141
2.43993
2.32843
0.64331
1.59352
0.87685
4.52280
1.93250
0.50675

0.07594
0.23517
0.31434
0.30668
0.54456
0.00083
0.40731
0.39023
0.32932
0.20641
0.49671
0.00327
0.40081
0.01095
0.12440

0.17575
0.07220
0.30155
0.26626
0.02744
0.05229
0.39508
0.31706
0.01098
0.13101
0.33967
0.02407
0.93487
0.29740
0.02881

0.01535
0.02186
0.02346
0.05651
0.07691
0.00207
0.12876
0.16791
0.17130
0.00824
0.44543
0.21012
0.49687
0.07540
0.06652

0.02
0.04
0.06
0.07
0.41
0.02
0.07
0.11
0.08
0.07
0.62
0.02
0.6
0.08
0.01
0.15
0.12

0.02
0.04
0.06
0.07
0.01
0.05
0.07
0.11
0.09
0.07
0.63
0.01
0.59
0.07
0.01
0.13
0.09

MTBE: methyl tert-butyl ether

Table 2
Parameters for the Redlich/Kister expansion for (qE )l for Group B data set.
Direct t minimizing the sum of squares of the pressure residuals
System

2-Butanone(1)/n-heptane(2) @ 45 C [27]
Benzene(1)/n-heptane(2) @ 80 C [11]
Methanol(1)/methylmethacrylate(2) @ 40 C [23]
Methanol(1)/methylmethacrylate(2) @ 50 C[23]
Chloroform(1)/1,4-dioxane(2) @ 50 C [25]
Pyridine(1)/tetrachloroethylene(2) @ 60 C [25]
n-Heptane(1)/2-pentanol(2) @ 75 C [29]
n-Heptane(1)/2-pentanol(2) @ 85 C [29]
n-Hexane(1)/dichloroethane(2) @ 50 C [21]
MTBE(1)/dichloromethane(2) @ 35 C [21]
Diethyl ketone(1)/n-hexane(2) @ 65 C [25]
Cyclohexane(1)/benzene(2) @ 40 C [24]
Ethanol(1)/n-hexane(2) @ 40 C [26]
MTBE(1)/chloroform(2) @ 40 C [28]
Methyl ethyl ketone(1)/toluene(2) @ 50 C [25]
Average
Average without diethyl ketone (1)/n-hexane(2) system

MRL: RMS P/kPa values from modied Raoults law (gamma/phi formulation with = 1).

the RMS P residuals1 are shown for each system. The average RMS
P residual for Group A is 0.06 kPa [2] and 0.15 kPa for Group B data
set (0.12 kPa without the DEK/nC6 system). The values shown under
MRL column header are from modied Raoults law (yi P = xi i Pisat )
for comparison purposes, wherein  i is found by Barker method
[11], yielding separate sets of 4PRK parameters. The two sets of
residuals for both groups A and B, are seen to be little different, and
demonstrate for a variety of highly nonideal systems that the EOSqE formulation for low pressure VLE data yields results comparable
to the best that can be obtained with the gamma/phi formulation.
Tables 3a and 3b show the three parameters of NRTL model
obtained with Barker method previously mentioned for Group A
and Group B data sets. The average RMS P residual are 0.26 kPa
and 0.23 kPa respectively, for Group A and for Group B data sets.
In spite of both residuals are greater than those obtained using the
4PRK model, in most cases are comparable with modied Raoults
law with average RMS P residual of 0.11 and 0.20 for Group
A and Group B data sets, respectively. The three parameters of
NRTL model for modied Raoults law are also obtained by Barker
method. Similar conclusion is obtained, with 2PNRTL model from
Tables 4a and 4b with average RMS P residuals of 0.44 kPa and
0.46 kPa Group A and Group B data sets respectively, with = 0.3
maintained as a constant.

n
1

RMS P: root mean square of P residuals =

i=1

P 2
i

For comparison, other formulations have been applied to all

Group A and Group B data sets. In all cases data reduction is
based on minimization of the sum of squares of the pressure residuals. Results for the average RMS P values are summarized as
follows:
Formaulting equation

Fitting procedure

RMSP (kPa) (a/b)

PR EOS
PR EOS
Modied Raoults law
PR EOS

qE with 4PRK Eq.

qE with Wilson Eq.
GE with 4PRK Eq.
HV mixing rules;
GE /RT with 4PRK Eq.
WS mixing rules;
GE /RT with 4PRK Eq.
WS mixing rules;
GE /RT with Wilson Eq.
qE with 3PNRTL Eq.
qE with 2PNRTL Eq.
GE with 3PNRTL Eq.
GE with 2P NRTL Eq.
HV mixing rules;
GE /RT with 3PNRTL Eq.
WS mixing rules;
GE /RT with 3PNRTL Eq.

0.06/0.13
0.32/0.28
0.06/0.15
3.62/2.09

PR EOS
PR EOS
PR EOS
PR EOS
Modied Raoults law
Modied Raoults law
PR EOS
PR EOS

0.61/0.44
0.60/0.47
0.22/0.26
0.44/0.46
0.11/0.20
0.23/0.34
3.74/3.23
0.71/0.74

where a: average RMS P for Group A data set [1230]; b: average

RMS P for Group B data set [11,2230].
Clearly, these formulations are less satisfactory than the Vidal
formulation using the PR EOS and qE correlation with the 4PRK

126

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

Table 3a
Parameters for 3PNRTL equation for (qE )l for Group A data set at 50 C.
Direct t minimizing the sum of squares of the pressure residuals
System

12

 12

 21

RMS P/kPa

MRL

Acetonitrile(1)/ethanol(2) [20]
Acetone(1)/ethanol(2) [13]
Acetone(1)/water(2) [16]
Acetone(1)/1,4-dioxane(2) [16]
Acetone(1)/chloroform(2) [19]
Acetone(1)/methanol(2) [19]
1,4-Dioxane(1)/water(2) [16]
Methanol(1)/chloroform(2) [19]
Ethanol(1)/chloroform(2) [14]
Ethanol(1)/1,4-dioxane(2) [14]
Chloroform(1)/1,4-dioxane(2) [14]
Chloroform(1)/n-heptane(2) [19]
Ethanol(1)/n-heptane(2) [19]
Ethanol(1)/water(2) [15]
Water(1)/ethylene glicol(2) [15]
Ethylene glicol(1)/ethanol(2) [15]
Acetonitrile(1)/water(2) [18]
Acetone(1)/ethylene glicol(2) [17]
Acetonitrile(1)/ethylene glicol(2) [17]
Average

0.076800
0.518030
0.407110
1.090130
0.387290
0.005850
0.092650
0.031600
0.231600
0.455640
0.077560
1.641820
0.584400
0.145940
0.946660
1.534430
0.308200
0.307140
0.538850

1.742670
0.649180
2.099770
0.092970
0.558080
2.951160
3.169470
2.908090
1.280230
1.424930
3.825920
0.291810
1.668840
3.334490
0.608880
0.151890
2.497490
2.170010
0.789530

0.428280
0.517850
1.308920
0.491180
1.315800
1.521180
1.229570
5.499580
3.280970
0.924560
1.479690
0.549010
1.593220
1.097030
0.877090
0.727540
1.495310
1.320260
1.382730

0.08
0.04
0.54
0.08
0.37
0.05
0.28
1.21
0.48
0.04
0.08
0.09
0.60
0.03
0.02
0.05
0.69
0.19
0.08
0.26

0.10
0.01
0.11
0.04
0.11
0.06
0.01
0.28
0.40
0.01
0.13
0.05
0.45
0.05
0.02
0.02
0.07
0.17
0.07
0.11

MRL: RMS P/kPa values from modied Raoults law (gamma/phi formulation with = 1).

equation, qE with 3 and 2PNRTL equation or the equivalent

gamma/phi correlation.
The ethanol/water data of Barr-David and Dodge [30] for 150
and 200 C also studied in our previous work [2] illustrates the
application of proposed EOS-qE method at high pressure. The
optima parameters that minimize the sum of squares of pressure
residuals, along with the RMS results for P and y1 of this correlation
are given in Table 5 for 3PNRTL, 2PNRTL models compared with
results obtained previously [2] of 3PRK expansion. All equations
compared resulted fully satisfactory to correlate these data within
their experimental precision, being slightly better the 3PNRTL
model for P correlation at lower temperature. In all cases 3PRK
model showed better results for y1 correlation. Fig. 1 through 3
display and compare the results of these correlations for the 200 C
data, including for comparison the WS mixing rules with 3PRK
for GE . Fig. 1 is a conventional Pxy diagram wherein different
upper lines represent calculated values of P versus experimental
x1 values, and lower lines represent the same values of P versus
calculated y1 values. Superimposed are the points corresponding to
correlated experimental values. Fig. 2 shows, for 3PNRTL and 3PRK

equations, the nature of related typical analytic correlations of qE .

The two upper lines represent calculated values of the partial propv

erties (q Ei ) versus x1 , (q Ei ) versus y1 for the liquid and vapor phase,

respectively. When combined by the summability
the par E equation

x q or qEv =
y q E )
tial properties for species 1 and 2 (qEl =
i i i
i i i
produce a line which passes exactly through all points for 3PRK
being the matches not so good for 3PNRTL model. These points
are values from the correlation, and show that the liquid and
vapor obey the same functional relationship and will be object
of further research. Fig. 3 displays the P and y1 residuals for
3PNRTL and 3PRK equations. The P values scatter appropriately
about zero and very close for both equations as a result of tting
Px data. The y1 values also show a reasonable scatter about
zero. Because the correlation is based solely on Px data, this
also is a pertinent test of the thermodynamic consistency of the
data.
The CO2 (1)/propane(2) system taken from the data of Reamer
et al. [31] also correlated by Urdaneta et al. [2] supplies a second illustrative and comparative application of proposed EOS-qE
method at high pressure. Correlation in this work is made by

Table 3b
Parameters for 3PNRTL equation for (qE )l for Group B data set.
Direct t minimizing the sum of squares of the pressure residuals
System

2-Butanone(1)/n-heptane(2) @ 45 C [27]
Benzene(1)/n-heptane(2) @ 80 C [11]
Methanol(1)/methylmethacrylate(2) @ 40 C [23]
Methanol(1)/methylmethacrylate(2) @ 50 C[23]
Chloroform(1)/1,4-dioxane(2) @ 50 C [25]
Pyridine(1)/tetrachloroethylene(2) @ 60 C [25]
n-Heptane(1)/2-pentanol(2) @ 75 C [29]
n-Heptane(1)/2-pentanol(2) @ 85 C [29]
n-Hexane(1)/dichloroethane(2) @ 50 C [21]
MTBE(1)/dichloromethane(2) @ 35 C [21]
Diethyl ketone(1)/n-hexane(2) @ 65 C [25]
Cyclohexane(1)/benzene(2) @ 40 C [24]
Ethanol(1)/n-hexane(2) @ 40 C [26]
MTBE(1)/chloroform(2) @ 40 C [28]
Methyl ethyl ketone(1)/toluene(2) @ 50 C [25]
Average
Average without correspondent outlier system

12

 12

 21

RCM P/kPa

MRL

0.61640
3.09142
0.28530
0.28053
0.07690
0.75198
0.36387
0.37007
0.04392
2.02676
0.06738
0.03522
0.03869
0.00236
0.34730

0.93320
0.21536
2.65082
2.57760
3.84576
0.58308
2.52714
2.32377
2.91791
0.66473
2.48397
1.36462
4.81509
1.88885
0.71611

1.02907
0.39077
1.86466
1.73596
1.49799
0.59480
1.48673
1.31998
0.67714
0.02146
4.54388
0.48210
0.24361
0.00002
0.26985

0.04
0.13
0.09
0.13
0.08
0.02
0.15
0.24
0.27
0.11
0.66
0.05
1.18
0.25
0.03
0.23
0.16

0.02
0.04
0.06
0.07
0.58
0.02
0.07
0.15
0.14
0.17
0.79
0.04
0.56
0.23
0.03
0.20
0.16

MRL: values from modied Raoults law (gamma/phi formulation with = 1).

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

127

Table 4a
Parameters for 2-parameter NRTL equation for (qE )l at 50 C.
Direct t minimizing the sum of squares of the pressure residuals
System

12

 12

 21

RMS P/kPa

MRL

Acetonitrile(1)/ethanol(2) [20]
Acetone(1)/ethanol(2) [13]
Acetone(1)/water(2) [16]
Acetone(1)/1,4-dioxane(2) [16]
Acetone(1)/chloroform(2) [19]
Acetone(1)/methanol(2) [19]
1,4-Dioxane(1)/water(2) [16]
Methanol(1)/chloroform(2) [19]
Ethanol(1)/chloroform(2) [14]
Ethanol(1)/1,4-dioxane(2) [14]
Chloroform(1)/1,4-dioxane(2) [14]
Chloroform(1)/n-heptane(2) [19]
Ethanol(1)/n-heptane(2) [19]
Ethanol(1)/water(2) [15]
Water(1)/ethylene glicol(2) [15]
Ethylene glicol(1)/ethanol(2) [15]
Acetonitrile(1)/water(2) [18]
Acetone(1)/ethylene glicol(2) [17]
Acetonitrile(1)/ethylene glicol(2) [17]
Average

0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3

1.17002
0.73078
2.36094
0.66658
0.45775
0.74560
2.18860
0.53309
1.21141
0.50967
2.02230
0.24861
2.10548
2.01522
1.29528
0.29493
2.52321
0.74687
0.64654

0.80374
0.49912
1.22206
0.27896
1.31351
0.57264
1.61826
2.55818
3.13214
1.03732
0.40212
1.24245
1.66659
0.62610
1.57022
0.68858
1.48835
1.40945
1.70107

0.11
0.05
0.93
0.05
0.38
0.10
0.33
2.36
0.57
0.15
0.14
0.34
0.95
0.30
0.07
0.10
0.69
0.43
0.22
0.44

0.13
0.09
0.81
0.04
0.11
0.06
0.06
0.29
0.35
0.03
0.13
0.06
1.20
0.05
0.02
0.04
0.39
0.31
0.18
0.23

MRL: RMS P/kPa values from modied Raoults law (gamma/phi formulation with = 1).

the 3 and 2PNRTL equations and compared with the 4PRK results
obtained in [2], also given in Table 5. The system at 277.59 K is
subcritical with measured vapor pressures, from which the qi are
calculated. Because the temperature of 310.93 K exceeds the critical
temperature of CO2 , no value of P1sat is available for evaluating q1 ,
being found it as an additional parameter to be tted in the regression procedure, similar to that followed in our previous work [2].
This gives q1 = 5.3523 with 4PRK as reported in [2], 5.3381 with
3PNRTL and 5.6245 with 2PNRTL equations. Fig. 4 shows results
for both temperatures on a Pxy diagram. The correlation is fully
satisfactory with all these equations for the 277.59 K data in spite
of the smaller number of parameters of NRTL equations. For comparison purposes, it was included the EOS-GE method with WS
mixing rules with the 3PRK equation, resulting with the worst
representation. However, at the supercritical 310.93 K condition,
the EOS-qE method with 4PRK and Wilson equations resulted in
a better correlation than 3 and 2PNRTL equations. At this condition convergence was not obtained when it was used the EOS-GE
method with WS mixing rules with any GE model. These results for
CO2 (1)/propane(2) data system were fully comparable with those
obtained by Orbey and Sandler [32].

The high pressure systems ethylene(1)/1-butene(2) of Jackson

and Wilsak [33] and propylene(1)/benzene(2) of Yamamoto et al.
[34] showed in Figs. 5 and 6, also were evaluated with the proposed EOS-qE method with 3 and 2PNRTL equations and compared
with 4PRK for the rst system and with 3PRK for the second system for data correlation. In Table 5 are showed results for adjusted
parameter and P and y1 residuals for 4 and 3PRK; 3 and 2PNRTL
equations. Because the ethylene is in supercritical condition, q1
value was obtained using the same adjusting procedure discussed
for CO2 /propane supercritical system, resulting 5.4473 when it was
used the 3PRK equation, 5.5090 for 3PNRTL and 5.4932 for 2PNRTL
models, respectively. Figs. 5 and 6 show the excellent correlation
agreement of all discussed models, including the Wilson and WS
mixing rules with 3 and 4PRK equation, respectively.
4. Prediction of behavior of ternary systems
When local composition equations (Wilson, NRTL, etc.,) are used
for correlation, predictions of Pxy behavior for ternary systems
may be based on data for the constituent binary systems for both
the EOS-GE and EOS-qE formulations. Reliable Px data at 50 C

Table 4b
Parameters for 2-parameter NRTL equation for (qE )l .
Direct t minimizing the sum of squares of the pressure residuals
System

12

 12

 21

RMS P/kPa

MRL

2-Butanone(1)/n-heptane(2) @ 45 C [27]
Benzene(1)/n-heptane(2) @ 80 C [11]
Methanol(1)/methylmethacrylate(2) @ 40 C [23]
Methanol(1)/methylmethacrylate(2) @ 50 C[23]
Chloroform(1)/1,4-dioxane(2) @ 50 C [25]
Pyridine(1)/tetrachloroethylene(2) @ 60 C [25]
n-Heptane(1)/2-pentanol(2) @ 75 C [29]
n-Heptane(1)/2-pentanol(2) @ 85 C [29]
n-Hexane(1)/dichloroethane(2) @ 50 C [21]
MTBE(1)/dichloromethane(2) @ 35 C [21]
Diethyl ketone(1)/n-hexane(2) @ 65 C [25]
Cyclohexane(1)/benzene(2) @ 40 C [24]
Ethanol(1)/n-hexane(2) @ 40 C [26]
MTBE(1)/chloroform(2) @ 40 C [28]
Methyl ethyl ketone(1)/toluene(2) @ 50 C [25]
Average

0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.4
0.3
0.3

1.05160
0.07721
1.03968
0.99263
2.08588
0.67373
0.69632
0.61285
1.38638
1.27473
1.02823
0.63074
2.29169
1.15041
0.76842

1.15254
0.81277
1.55276
1.54945
0.21775
0.63794
1.48747
1.45629
0.66057
0.80929
2.85774
0.21465
1.38085
1.10100
0.32440

0.11
0.67
0.32
0.44
0.59
0.02
0.61
0.78
0.42
0.14
0.99
0.05
1.50
0.29
0.03
0.46

0.84
0.06
0.24
0.31
0.57
0.03
0.42
0.43
0.14
0.17
0.84
0.05
0.80
0.24
0.03
0.34

MRL: RMS P/kPa values from modied Raoults law (gamma/phi formulation with = 1).

128

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

Table 5
VLE correlations for high-pressure systems, for different models t of qE .
T/K (P Range/bar)

Model

P0

P1

P2

P3

q1

q2

RMS P

RMS y

0.11
0.08
0.09
0.27
0.33
0.34

0.008
0.030
0.030
0.007
0.026
0.028

0.05
0.16
0.39
0.03
0.30
0.04

0.005
0.011
0.006
0.014
0.016
0.044

10.34026

0.12
0.16
0.26

0.009
0.024
0.017

8.0335

0.03
0.04
0.05

0.002
0.001
0.002

Ethanol(1)/water(2) [30]: b1 = 54.0666; b2 = 18.9527

423.15
(510)
473.15
(1530)

3PRKa
3PNRTL
2PNRTL
3PRKa
3PNRTL
2PNRTL

2.9340
0.2801
0.3000
2.8257
0.4214
0.3000

1.1157
2.2348
2.1696
0.9509
1.8020
2.0907

4PRKa
3PNRTL
2PNRTL
4PRKa
3PNRTL
2PNRTL

2.2266
1.0862
0.3000
1.3263
0.3000
0.3000

0.5674
0.5593
0.0076
0.0987
0.5992
0.2578

3PRK
3PNRTL
2PNRTL

0.12104
0.30000
0.30000

0.6204
0.3346
0.3837
0.8211
0.6257
0.4389

8.9319

12.2194

7.0667

10.2118

6.8538

9.1316

5.3523b
5.3381b
5.6245b

7.7121

CO2 (1)/propane(2) [31]: b1 = 26.6556; b2 = 56.2848

277.59
(540)
310.93
(1570)

0.3392
0.9883
1.7714
0.2429
0.6020
1.6530

0.2604

0.1827

Ethylene(1)/butene(2) [33]: b1 = 36.3073; b2 = 67.2366

293.15
(2.555)

0.20023
0.27620
0.51790

0.16932
0.08232
0.41522

5.4473b
5.5090b
5.4932b

Propylene(1)/benzene(2) [34]: b1 = 74.2388; b2 = 51.0977

298.15
(0.112)
a
b

4PRK
3PNRTL
2PNRTL

0.7923
2.7610
0.3000

0.0109
0.0770
0.2909

0.0834
0.6177
0.4748

0.1316

15.7238

These parameters were determined in our previous work [2].

Value tted with corresponding model equation parameters Pi , i = 0,3; For RK model, Pi = Ai ; for NRTL Model, P0 = , P1 =  12 and P2 =  21 .

are available for 8 ternary systems [1220] formed from the 19

constituent binaries (Group A data set) reported in Table 1 of our
previous work [2] with all required properties. Regressions of each
binary data set with the 3PNRTL for EOS-GE and EOS-qE formulations, yield sets of parameters (,  12 and  21 ) and resulting RMS
P values listed in Table 6 in which EOS-qE formulation parameters

are also showed in Table 3b and are repeated here for comparisons purposes. The NRTL parameters for both correlations EOS-QE
and EOS-QE are very different, but the overall results showed are
as good as those obtained with the Wilson equation for qE representation and better than those for GE , the two latest calculated
in our previous work [2], with average RMS P = 0.32 and 0.23 kPa

Fig. 2. qE Functions and its partial components for the ethanol/H2 O system at 200 C [30] given by 3PNRTL and 3PRK.

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

129

Table 6
Parameters of 3PNRTL equations and correlation results for binary systems at 50 C.
System

NRTL equation
GE correlation

qE correlation

12
21

RMS P/kPa

12
21

RMS P/kPa

Acetonitrile(1)/ethanol(2) [20]

0.6206

0.10

0.0768

0.9505

0.01

0.51803

Acetone(1)/water(2) [16]

0.4908

0.11

0.4071

Acetone(1)/1,4-dioxane(2) [16]

1.0764

0.04

1.0901

Acetone(1)/chloroform(2) [19]

0.1685

0.11

0.3873

Acetone(1)/methanol(2) [19]

0.0044

0.06

0.0059

1,4-Dioxane(1)/water(2) [16]

0.4321

0.01

0.0927

Methanol(1)/chloroform(2) [19]

0.4226

0.28

0.0316

Ethanol(1)/chloroform(2) [14]

0.7246

0.40

0.2316

Ethanol(1)/1,4-dioxane(2) [14]

1.0024

0.01

0.4556

Chloroform(1)/1,4-dioxane(2) [14]

0.2428

0.13

0.0776

Chloroform(1)/n-heptane(2) [19]

0.6056

0.05

1.6418

Ethanol(1)/n-heptane(2) [19]

1.3757

0.45

0.5844

Ethanol(1)/water(2) [15]

0.2994

0.04

0.1381

Water(1)/ethylene glicol(2) [15]

6.9458

0.02

1.0950

Ethylene glicol(1)/ethanol(2) [15]

1.2141

0.02

1.5344

Acetonitrile(1)/water(2) [18]

0.8975

0.07

0.3082

Acetone(1)/ethylene glicol(2) [17]

0.4057

0.17

0.3071

Acetonitrile(1)/ethylene glicol(2)
[17]
Average

0.4231

0.07

0.5389

1.7427
0.4283
0.6492
0.5179
2.0998
1.3089
0.0930
0.4912
0.5581
1.3158
2.9512
1.5212
3.1695
1.2296
2.9081a
5.4996
1.2802
3.2810
1.4249
0.9246
3.8259
1.4797
0.2918
0.5490
1.6688
1.5932
2.7799
0.0167
0.3459
0.7615
0.1519
0.7275
2.4975
1.4953
2.1700
1.3203
0.7895
1.3827

0.08

Acetone(1)/ethanol(2) [13]

0.6581
0.8777
0.38341
0.49553
1.0124
1.6162
0.3310
0.1472
1.2879
0.6629
1.3346
1.9880
1.1719
1.2716
0.5648
1.4002
0.9983
0.3798
0.2797
0.4846
0.6768
1.4308
0.8121
0.8101
0.7913
0.6962
0.6731
1.5010
0.1527
0.1233
0.3489
0.2588
0.8714
0.6446
1.3606
0.8190
1.6436
0.8130

0.11

respectively vs. average RMS P = 0.32 and 0.11 kPa, obtained in

this work, respectively. Substitutions of the appropriate binary
parameters into the NRTL equations written for the ternary systems
provide direct prediction of ternary behavior for both formulations.
Results for all 8 ternary systems studied in present work using
the NRTL equation are reported in Table 7. For each pure species
the bi values, vapor pressure and qi calculated values, are given in
Tables 1 and 5 our previous work [2]. Correlations results based on

Table 7
Results of VLE calculations for ternary systems at 50 C.
System

Acetonitrile(1)/ethanol(2)/water(3) [20]
1,4-Dioxane(1)/ethanol(2)/water(3) [12]
Acetone(1)/ethanol(2)/water(3) [13]
Acetone(1)/1,4-dioxane(2)/water(3) [16]
Ethanol(1)/chloroform(2)/1,4-dioxane(3) [14]
Water(1)/ethylene glycol(2)/ethanol(3) [15]
Ethylene glycol(1)/acetone(2)/water(3) [18]
Ethylene glycol(1)/acetonitrile(2)/water(3) [18]
Average
Average without atypical values (outlier)

RMS P/kPa
EOS-qE
3PNRTL

EOS-qE
2PNRTL

1.12
1.23
0.80
0.77
8.27
0.47
1.44
0.43
1.81
0.89

0.52
0.77
0.94
0.92
10.33
0.75
0.87
0.52
1.95
0.76

0.04
0.54
0.08
1.32
0.05
0.28
1.24
0.48
0.04
0.08
0.09
0.60
0.20
0.02
0.05
0.69
0.19
0.08
0.32

the 2P and 3PNRTL equations, values of RMS P are presented for the
EOS-qE formulation and compared with those obtained with Wilson model in [2]. Results on the whole are comparable, though the
NRTL neither Wilson equations are evidently not particularly well
suited for representation of qE for ethanol/chloroform/1,4-dioxane.
Greater average RMS P values were obtained using EOS-qE formulation with NRTL equations comparing with EOS-GE formulation
with WS mixing rules when all results in our previous work [2]
were considered (EOS-qE formulation with: 3PNRTL Eq.: 1.81 kPa;
2PNRTL Eq.: 1.95 kPa; Wilson: 1.34 kPa; EOS-GE formulation with
WS mixing rules and Wilson Eq.: 1.01 kPa; Modied Roults law
with Wilson Eq.: 0.94 kPa) When the extreme or atypical RMS P
values are excluded, the average RMS P values obtained using
EOS-qE formulation were reasonably smaller and comparable (EOSqE formulation with: 3PNRTL Eq.: 0.89 kPa; 2PNRTL Eq.: 0.76 kPa;
Wilson Eq.: 0.64 kPa; EOS-GE formulation with WS mixing rules
and Wilson Eq.: 1.00 kPa; modied Roults law with Wilson Eq.:
0.93 kPa)
5. Effect of temperature
Thermodynamics provides exact equations relating the temperature dependence of both GE and qE to the excess enthalpy HE in
order to predict the not available experimental VLE information.

130

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

3PNRTL
3PRK
2PNRTL
Wilson
WS-3PRK
Experimental Values
Critical Point

60

Pressure (bar)

50
40
30
20
10
0
0,0

Fig. 3. Residuals in P and y1 from t of ethanol/H2 O Px1 data at 200 C [30].

Rigorous application requires integration over a temperature range,

which can be done only when all data is available, and they are
seldom fully adequate if exist. Alternatively empirical procedures
are used that may sometimes be acceptable. Orbey and Sandler
[32] show examples of EOS-GE correlations based on WS mixing
rules with parameters for GE /RT and ln i evaluated at one temperature and used unchanged at another. There is, however, no evident
theoretical justication for the underlying presumption that these
parameters are independent of T and it may be only approximately
valid in some instances. A similar empirical procedure with the
EOS-qE formulation is based on the assumption that the product qE
T is constant. Application with the Wilson, NRTL or Redlich/Kister
correlating equations is then particularly simple, requiring only
that the any of the parameters Ki (= 12 or 21 when i = 0; = ,
 12 or  21 ; when i = 1, in this work) at two temperatures (T and T0 )
be inversely related to the temperatures. Thus,
Ki (T ) = Ki (T0 )

70

(11)

4PRK
3PNRTL
2PNRTL
Wilson
Experimental Values 310.95 K
Experimental Values 277.59 K
Critical Point

50
40

277.59 K

20

0,8

1,0

3PNRTL
4PRK
2PNRTL
Wilson
WS-4PRK
Experimental Values

10

30

0,6

There is no theoretical basis supporting this procedure, but it is

often satisfactory over relatively small temperature intervals.
Application of this constant qE T product assumption to the 3
and 2-parameters NRTL compared with 2-parameter Redlich/Kister
equations to the acetone(1)/methanol(2) experimental data system
[19,35] produces results for four temperatures showed in Table 8.
The rst two lines for each temperature show that results from the
gamma/phi and EOS-qE formulations are equivalent and excellent.
Computational effort is about the same, but the EOS-qE formulation treats both phases exactly alike, without additional required
information. Table 9 provides parameters for the direct correlation
of qE for the four temperatures for 3 and 2PNRTL and those for
2PRK equations are taken from Table 7 of Urdaneta et al. [2]. At
323.15 K, the EOS-GE formulation based on WS mixing rules is only
satisfactory.
As expected, the two predictions at the three higher temperatures are inferior to the direct-t procedures, with those also taken
from Table 6 of Urdaneta et al. [2] based on the Orbey/Sandler
assumption of temperature-independent parameters, markedly

12

310.95 K

0,4

Mole Fraction (x1,y1)

Fig. 5. Experimental values [33] and correlated Pxy curves for ethylene/butene at
290 K. PRSV EOS with qE given by 3PRK, 3P and 2PNRTL, Wilson and WS-3PRK models
with parameters tted to Px Data

Pressure (bar)

60

Pressure (bar)

T0
T

0,2

10

0,0

0,2

0,4

0,6

Mole Fraction, x1, y1

0,8

1,0

Fig. 4. Experimental values [31] and correlated Pxy curves for CO2 /propane at
277.59 K and 310.95 K. Peng/Robinson EOS with qE given by models in legends tted
to Px data.

0,0

0,2

0,4

0,6

0,8

1,0

Mole fraction (x1, y1)

Fig. 6. Experimental values [34] and correlated Pxy curves for propylene/benzene
at 298.15 K. PRSV EOS with qE given by 3P and 2PNRTL, 4PRK, Wilson and WS-4PRK
models with parameters tted to Px data.

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

131

Table 8
EVL Prediction from a different temperature.
T (K) (P (kPa))

Formulation/procedure

RMS P (kPa)

RMS y

323.15 (5684)

Gamma/phireported by Walsh [19]

EOS-qE direct correlation of qE -3PNRTL
EOS-qE direct correlation of qE -2PNRTL
Gamma/phireported by Wilsak et al. [35]
EOS-qE direct correlation of qE -3PNRTL
EOS-qE direct correlation of qE -2PNRTL
EOS-qE -3PNRTLpredicted from correlation at 323.15 Ka
EOS-qE -2PNRTLpredicted from correlation at 323.15 Ka
Gamma/Phireported by Wilsak et al. [35]
EOS-qE direct correlation of qE -3PNRTL
EOS-qE direct correlation of qE -2PNRTL
EOS-qE -3PNRTLpredicted from correlation at 323.15 Ka
EOS-qE -2PNRTLpredicted from correlation at 323.15 Ka
Gamma/Phireported by Wilsak et al. [35]
EOS-qE direct correlation of qE -3PNRTL
EOS-qE direct correlation of qE -2PNRTL
EOS-qE -3PNRTLpredicted from correlation at 323.15 Ka
EOS-qE -2PNRTLpredicted from correlation at 323.15 Ka

0.09
0.05
0.10
0.83
0.59
0.77
3.78
1.38
1.39
0.73
1.18
5.11
4.49
2.38
2.32
3.28
5.56
12.78

0.006
0.009
0.007
0.007
0.007
0.013
0.011
0.011
0.013
0.013
0.006
0.005
0.006
0.005
0.008

372.8 (365405)

397.7 (667783)

422.6 (11211399)

Acetone(1)/methanol(2) correlated by 3PNRTL equation.

a
Based on correlation qE a 323.15 K from suposition about qE XT is constant.

Table 9
Direct Correlation of qE by NRTL equation.
3PNRTL
T (K)

 12

 21

q1

q2

323.15
372.8
397.7
422.6

0.00585
0.04426
0.06113
0.00954

2.95116
1.63393
1.55196
3.34041

1.52118
0.42371
0.45537
2.34363

12.5605
10.0317
9.0174
8.1570

14.2614
11.1172
9.8612
8.7902

2PNRTL
T (K)

 12

 21

q1

q2

323.15
372.8
397.7
422.6

0.30000
0.30000
0.30000
0.30000

0.74560
0.82046
0.74560
0.82437

0.57264
0.32201
0.57264
0.12457

12.5605
10.0317
9.0174
8.1570

14.2614
11.1172
9.8612
8.7902

less successful than those based the assumption of constancy of

the product qE T. Also, it is showed than prediction with 3 and
2PNRTL was highly satisfactory, having the same or even better
representation performance than 2PRK.

3PNRTL
2PNRTL
3PRK
Experimental Tx1 Values

338

Temperature ( K)

336

Experimental Ty1 Values

334

332

330

Calculation of a Txy relationship at constant pressure is easily

undertaken using Eq. (11) for parameters estimating at required
temperature. For the acetone(1)/methanol(2) experimental data
system at 101.325 kPa [36] produces the result shown by Fig. 7. For
2PRK expansion, the RMS y and RMS T values are 0.002 and 0.13 K;
for 3PNRTL, 0.003 and 0.20 K and for 2PNRTL, 0.002 and 0.16 K,
respectively. Temperature dependence of parameter q and PR EOS
parameters (ai , bi and qi ) calculations are detailed in our previous
work [2]. It was obtained an excellent representation of experimental data at 101.325 kPa, correlation quality also related to the small
differences between calculated temperatures and 323.15 K [36],
being results for all models comparable. Also, it was obtained that
Redlich/Kister resulted slightly better than 2PNRTL, and that the
3PNRTL resulted slightly worse than 2PNRTL for this experimental
data system. All models showed a small temperature underestimation in the mid-range of x1 mole fraction.
6. Concluding remarks

328
0,0

0,2

0,4

0,6

0,8

1,0

Mole Fraction (x1, y1)

Fig. 7. Experimental values [36] and correlated Txy curves for acetone/methanol at
101.325 kPa. Peng/Robinson EOS with qE given by application Eq. (11) to 3PNRTL,
2PNRTL and 3PRK equations based on experimental data at 323.15 K.

The proposed extended Vidal formulation EOS-qE for VLE calculations with 3 and 2PNRTL equation resulted satisfactory compared
with gamma-phi formulation using modied Raoult law and with
EOS-GE formulation based on WS mixing rules for the low pressure 34 isothermal binary experimental data systems using the
corresponding NRTL equation.
For the isothermal high pressure binary systems experimental 5 data sets studied, results of the proposed extended Vidal

132

M.R. Urdaneta P. / Fluid Phase Equilibria 365 (2014) 123132

formulation as EOS-qE using 3 and 2PNRTL, were in their experimental precision range. Both models allowed results reasonably
satisfactory, even when one of species is at supercritical conditions,
in which case, qi is obtained as an adjusting parameter.
Results corresponding to the low pressure ternary systems
experimental 8 data sets studied using the proposed extended
Vidal formulation as EOS-qE using 3 and 2PNRTL proposed in
this work were comparable with the gamma-phi formulation
with the modied Raoults law, using 3 and 2PNRTL equations
for GE calculations and also comparable with EOS-GE formulation with WS mixing rules with Wilson equation obtained in our
previous work [2], with the exception for ethanol/chloroform/1,4dioxane.
For the acetone/methanol experimental data set reported by
various authors, VLE prediction at other temperature using the qE XT
proposed assumption yielded better results than Orbey/Sandler
supposition of temperature parameter constancy and Txy correlation based on proposed EOS-qE model resulted within the
experimental precision when 3 and 2-parameter NRTL was compared with 2PRK.
Acknowledgements
This work try to honor the memory of Prof. Hendrick Van Ness,
who inspired and guided me in this, previous and other future
research in this area.
The author would like to thank to the Consejo de Desarrollo
Cientco y Humanstico (CONDES) de LUZ, Venezuela, for nancial
support.
References
[1] J.O. Valderrama, The state of the cubic equations of state, Ind. Eng. Chem. Res.
42 (2003) 16031618.
[2] M.R. Urdaneta, L.R. Fernndez, H.C. Van Ness, Reappraisal of the Vidal equationof-state formulation for vapor/liquid equilibrium, Fluid Phase Equilib. 264
(2008) 242252.
[3] J. Vidal, Mixing rules and excess properties in cubic equations of state, Chem.
Eng. Sci. 33 (1978) 787791.
[4] O. Redlich, A.T. Kister, Algebraic representation of thermodynamic properties and the classication of solutions, Ind. Eng. Chem. 40 (1948)
345348.
[5] H. Renon, J.M. Prausnitz, Estimation of parameters for the NRTL equation for
excess Gibbs energies of strongly nonideal liquid mixtures, Ind. Eng. Chem.
Process Des. Dev. 8 (1969) 413419.
[6] M.-J. Huron, J. Vidal, New mixing rules in simple equations of state for representing vapour-liquid equilibria of strongly non-ideal mixtures, Fluid Phase
Equilib. 3 (1979) 255271.
[7] D.S.H. Wong, S.I. Sandler, A theoretically correct mixing rule for cubic equations
of state, AIChE J. 38 (1992) 671680.
[8] H.C. Van Ness, M.M. Abbott, Classical Thermodynamics of Nonelectrolyte Solutions: With Applications to Phase Equilibria, McGraw-Hill, 1982.
[9] D.Y. Peng, D.B. Robinson, A new two constant equation of state Ind. Eng. Chem.,
Fundam. 15 (1976) 5964.
[10] R. Stryjek, J.H. Vera, PRSV an improved peng-Robinson equation of state with
new mixing rules for strongly nonideal mixtures, Can. J. Chem. Eng. 64 (1986)
334340.
[11] J.A. Barker, Determination of activity coefcients from total pressure measurements, Aust. J. Chem. 6 (1953) 207210.
[12] A.M. Balcazar-Ortiz, R.B. Patel, M.M. Abbott, H.C. Van Ness, Excess thermodynamic functions for ternary systems. 5. Total-pressure data and GE for
1,4-dioxane-ethanol-water at 50. degree. C, J. Chem. Eng. Data 24 (1979)
133136.

[13] M.M. Chaudhry, H.C. Van Ness, M.M. Abbott, Excess thermodynamic functions
for ternary systems. 6. Total-pressure data and GE for acetone-ethanol-water
at 50. degree. C, J. Chem. Eng. Data 25 (1980) 254257.
[14] C. Gonzalez, H.C. Van Ness, Excess thermodynamic functions for ternary systems. 8. Total-pressure data and GE for ethanol/chloroform/1, 4-dioxane at 50.
degree. C, J. Chem. Eng. Data 28 (1983) 407409.
[15] C. Gonzalez, H.C. Van Ness, Excess thermodynamic functions for ternary systems. 9. Total-pressure data and GE for water/ethylene glycol/ethanol at 50.
degree. C, J. Chem. Eng. Data 28 (1983) 410412.
[16] J.R. Loehe, H.C. Van Ness, M.M. Abbott, Excess thermodynamic functions for
ternary systems. 7. Total pressure data and GE for acetone/1, 4-dioxane/water
at 50. degree. C, J. Chem. Eng. Data 26 (1981) 178181.

[17] M.A. Villamann,

A.A.J. Allawi, H.C.V. Ness, Int. Data Ser. A (1984) 6.

[18] M.A. Villamanan,

A.J. Allawi, H.C. Van Ness, Excess thermodynamic functions for ternary systems. 11. Total-pressure data and GE for ethylene
glycol/acetone/water and for ethylene glycol/acetonitrile/water at 50. degree.
C, J. Chem. Eng. Data 29 (1984) 293296.
[19] G.E.J. Walsh, Experimental determination of vapor-liquid equilibria for two
ternary systems, in: Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy NY 12180, 1974.
[20] S.R. Wilson, R.B. Patel, M.M. Abbott, H.C. Van Ness, Excess thermodynamic function for ternary systems. 4. Total-pressure data and GE for
acetonitrile-ethanol-water at 50. degree. C, J. Chem. Eng. Data 24 (1979)
130132.
[21] S.K. Chaudhari, S.S. Katti, Vapourliquid equilibria of binary mixtures of nhexane, n-heptane and n-octane with 1,2-dichloroethane at 323.15 K, Fluid
Phase Equilib. 57 (1990) 297306.
[22] V. Fried, P. Gallant, G.B. Schneier, Vapor-liquid equilibrium in the
system pyridine-tetrachloroethylene, J. Chem. Eng. Data 12 (1967)
504508.
[23] T. Ishikawa, B.C.Y. Lu, Vapor-liquid equilibria of the methanol-methyl
methacrylate system at 313.15, 323.15 and 333.15 K, Fluid Phase Equilib. 3
(1979) 2334.

Vapor-liquid equilib[24] L.M. Lozano, E.A. Montero, M.C. Martn, M.A. Villamann,
ria of binary mixtures containing methyl tert-butyl ether (MTBE) and/or
substitution hydrocarbons at 298.15 K and 313.15 K, Fluid Phase Equilib. 110
(1995) 219230.
[25] J.M. Smith, H.C.V. Ness, M.M. Abbott, Introduction to Chemical Engineering
Thermodynamics, 7th ed., McGraw-Hill, 2005.
[26] H. Sugi, T. Katayama, Ternary liquidliquid and miscible binary vapourliquid
equilibrium data for the two systems n-hexane ethanol acetonitrile
and water acetonitrileethyl acetate, J. Chem. Eng. Jpn. 11 (1978)
167172.
[27] M. Takeo, K. Nishi, T. Nitta, T. Katayama, Isothermal vaporliquid equilibria for
two binary mixtures of heptane with 2-butanone and 4-4-methyl-2-pentanone
measured by a dynamic still with a pressure regulation, Fluid Phase Equilib. 3
(1979) 123131.
[28] H.C. Van Ness, Thermodynamics in the treatment of vapor/liquid equilibrium
(VLE) data, Pure Appl. Chem. 67 (1995) 859872.
[29] J. Wolfov, J. Linek, I. Wichterle, Vapourliquid equilibria in the heptane2pentanol and heptane2-methyl-1-butanol systems at 75, 85 and 95 C, Fluid
Phase Equilib. 64 (1991) 281289.
[30] F. Barr-David, B.F. Dodge, Vapor-Liquid, Equilibrium at high pressures. The
systems ethanol-water and 2-propanol-water, J. Chem. Eng. Data 4 (1959)
107121.
[31] H.H. Reamer, B.H. Sage, W.N. Lacey, Phase equilibria in hydrocarbon systems.
Volumetric and phase behavior of the propane-carbon dioxide system, Ind. Eng.
Chem. 43 (1951) 25152520.
[32] H. Orbey, S.I. Sandler, Modeling VaporLiquid Equilibria: Cubic Equations of
State and Their Mixing Rules, Cambridge University Press, 1998.
[33] P.L. Jackson, R.A. Wilsak, Thermodynamic consistency tests based on the
GibbsDuhem equation applied to isothermal, binary vaporliquid equilibrium data: data evaluation and model testing, Fluid Phase Equilib. 103 (1995)
155197.
[34] H. Yamamoto, K. Ohgaki, T. Katayama, Isothermal vapour-liquid equilibrium
data of the benzene-propylene system at 25 C, Fluid Phase Equilib. 46 (1989)
5358.
[35] R.A. Wilsak, S.W. Campbell, G. Thodos, Vaporliquid equilibrium measurements for the methanolacetone system at 372.8, 397.7 and 422.6 K, Fluid
Phase Equilib. 28 (1986) 1337.
[36] J. Gmehling, U. Onken, W. Arlt, P. Grenzheuser, U. Weidlich, B. Kolbe, J. Rarey,
Vapor-Liquid Equilibrium Data Collection, DECHEMA, 1988.