Fluid Phase Equilibria 224 (2004) 111118

Vaporliquid equilibrium of systems containing alcohols, water, carbon

dioxide and hydrocarbons using SAFT
Xiao-Sen Li, Peter Englezos
Department of Chemical and Biological Engineering, The University of British Columbia, 2216 Main Mall, Vancouver, BC, Canada V6T 1Z4
Received 9 January 2004; received in revised form 17 June 2004; accepted 18 June 2004
Available online 31 July 2004

Abstract
The statistical associating fluid theory (SAFT) equation of state is employed for the correlation and prediction of vaporliquid equilibrium (VLE) of eighteen binary mixtures. These include water with methane, ethane, propane, butane, propylene, carbon dioxide, methanol,
ethanol and ethylene glycol (EG), ethanol with ethane, propane, butane and propylene, methanol with methane, ethane and carbon dioxide and finally EG with methane and ethane. Moreover, vaporliquid equilibrium for nine ternary systems was predicted. The systems
are water/ethanol/alkane (ethane, propane, butane), water/ethanol/propylene, water/methanol/carbon dioxide, water/methanol/methane, water/methanol/ethane, water/EG/methane and water/EG/ethane. The results were found to be in satisfactory agreement with the experimental
data except for the water/methanol/methane system for which the root mean square deviations for pressure were 6068% when the methanol
concentration in the liquid phase was 60 wt.%.
2004 Elsevier B.V. All rights reserved.
Keywords: Vaporliquid equilibrium; SAFT; Alcohol; Alkane; Water

1. Introduction
The modeling of phase behavior and the calculation of
thermodynamic properties of aqueous solutions involving alcohols, hydrocarbon, water and carbon dioxide is of considerable industrial importance. For example, such information is needed for the design of facilities for the extraction
of alcohols from aqueous solutions using near critical light
hydrocarbons as solvents [1,2]. Another application is the inhibition of gas hydrate formation in the oil and gas industry
[3]. Mixtures containing associating compounds are also of
interest from a theoretical point of view for testing molecular
thermodynamic models.
One successful modelling approach is the statistical associating fluid theory (SAFT), which is based on Wertheims
first-order thermodynamic perturbation theory for associating fluids [4-8]. SAFT has been used to model successfully a
Corresponding author. Tel.: +1 604 822 6184; fax: +1 604 822 6003.
E-mail address: englezos@interchange.ubc.ca (P. Englezos).

0378-3812/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.06.052

wide variety of the thermodynamic properties and phase equilibria for industrially important fluids [9]. Huang and Radosz
[6] applied the original SAFT to calculate the phase equilibria of water/n-alkane, water/methane and water/ethane, and
hydrocarbon/alcohol mixtures. It is noted that for the water/methane and water/ethane systems they only calculated
the solubility of water in the hydrocarbon-rich phase. Kraska
and Gubbins [10] proposed the LennardJones (LJ)-SAFT,
in which the chain segments were treated as LennardJones
spheres, to correlate the solubility of water in methane and
in ethane and the equilibria in 1-alkanol/n-alkane systems.
The results with LJ-SAFT exhibited better agreement with
experimental data than the original SAFT [10]. Galindo et al.
[11] applied the hard-sphere (HS)-SAFT to model the critical behaviour of n-alkane/water mixtures, and good agreement with experimental data was obtained. In this equation,
molecules are treated as chains of hard-sphere segments with
van der Waals interactions. Garcia-Lisbona et al. [12] also
used HS-SAFT to predict the high-pressure phase equilibria
of binary aqueous solutions of 1-butanol, n-butoxyethanol

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X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

and n-decylpentaoxyethylene ether. In additon, Voutsas et

al. [13] compared the original SAFT with the Cubic-PlusAssociation Equation of State (CPA EoS) for the phase equilibria of the n-alkane/water systems. Application of the two
equations of state to the correlation of water/methane and
water/ethane VLE showed that both models computed satisfactorily the solubility of water in hydrocarbon phase. On
the other hand the SAFT model was not able to adequately
calculate the solubilities in the water phase whereas the CPA
EoS resulted in a fair agreement with the experimental data.
The authors pointed to the need for a better physical term
for the SAFT equation [13]. Recently, McCabe et al. [14]
studied the unexpected shift in the solubility of n-alkanes in
near critical water where longer n-alkane molecules are more
soluble than shorter ones by using HS-SAFT. The prediction
of the anomalous behaviour was excellent.
In previous work, we used the original SAFT equation to model the phase equilibria of the ternary systems, water/alcohol/alcohol, and the constituent subsystems [15]. In this work, we applied the above SAFT
for the correlation and prediction of Vaporliquid equilibria of binary mixtures of alcohols with n-alkanes, propylene, water and carbon dioxide. Furthermore, we employed the SAFT to predict high pressure VLE in ternary
systems, water/ethanol/n-alkane (ethane, propane and butane), water/ethanol/propylene, water/methanol/carbon dioxide, water/methanol/methane, water/methanol/ethane, water/EG/methane and water/EG/ethane. It is noted that there
are no other applications of SAFT to VLE of the water/alcohol/hydrocarbon ternary mixtures. However, ternary
LLE calculations were done for the waterethanolbenzene
system [16]. Water/hydrocarbon systems exhibit extremely
nonideal behaviour due to the difference in the nature of
intermolecular forces between water and the hydrocarbon
molecules [2]. A different procedure was used to obtain segment parameter values for methane, ethane, propane, butane,
propylene and carbon dioxide in order to ensure satisfactory
representation of binary water/hydrocarbon VLE data

2. Equation of State
The residual Helmholtz free energy for an n-component
mixture of associating chain molecules can be expressed as
the sum of hard sphere repulsion, hard chain formation, dispersion and association terms as follows
Ares = A Aid = Ahs + Achain + Adisp + Aassoc

(1)

where Aid is the free energy of an ideal gas with the same
density and temperature as the system, Ahs the free energy of a hard-sphere fluid relative to the idea gas. The
Ahs term is calculated with the BoublikMansoori
CarnahanStarlingLeland equation [17,18] and the
BarkerHenderson perturbation theory [19]. Detailed
expressions for this and the other free energy terms in Eq.

(1) are given elsewhere [15]. Achain is the free energy when
chains are formed from hard spheres. This chain term was
derived by Chapman et al. [7]. Adisp and Aassoc are the
contributions to the free energy of dispersion and association
interactions, respectively. This dispersion term is calculated
by using an expression based on the LennardJones potential
[19]. The following combining rules are used for the cross
parameters between different segments, ij and ij
ii + jj
2

ij = (1 kij ) ii jj

ij =

(2)
(3)

where ii or jj is the soft-sphere diameter of segment i or

j, ii or jj is the energy parameter of the LJ potential of
segment i or j, kij is binary interaction parameter.
The Helmhotz energy due to association is calculated by
an expression of Chapman et al. [8]. For cross-associating
mixtures, we have the mixing rules [8]:
Ai Bi + Aj Bj
2


= (1 kijAB ) (Ai Bi Aj Bj )

Aj Bi = Ai Bj =

(4)

Aj Bi = Ai Bj

(5)

where AB is the bonding volume and AB /k as the associating

energy. kijAB is binary associating interaction parameter.
The calculation of VLE was performed by following the
procedure described elsewhere [15].

3. Pure component and binary interaction parameter

estimation
The SAFT equation requires three pure-component parameters for non-associating fluids and five parameters for
associating fluids. These parameters are the LennardJones
(LJ) potential well depth (/k), the soft sphere diameter of
segments (), the number of segments of the molecule (m),
the bonding volume (AB ) and the association energy between sites A and B (AB ). These parameters can be estimated
from the regression of saturated vapor pressure and liquid
density data. In this work, the segment parameters (/k, , m,
AB , AB ) for water, ethanol, methanol, EG, methane, ethane,
propane, butane, propylene, and carbon dioxide need to be
obtained for the correlation and prediction of the corresponding binary and ternary mixtures. The parameters for water,
methanol, ethanol, EG and were obtained by simultaneously
fitting the experimental saturated vapour pressures and liquid
densities available in the literature [20,21] as given in Table
1. A different procedure was used to estimate the segment parameters of methane, ethane, propane, butane, propylene and
carbon dioxide. In particular, binary hydrocarbon/water VLE
data were used to estimate the segment parameters. Huang
and Rodosz [5] also reported pure compound parameters for
the SAFT equation. They employed the square well potential one for the dispersion term [5,6]. We used their reported

X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

113

Table 1
Estimated segment parameters for pure fluids
Fluid

T (K)

(1010 m)

/k (k)

AB /k (K)

AB

Water
Methanol
Ethanol
EG
Methane
Ethane
Propane
Butane
Propylene
CO2

283483
295489
303503
375496
523
523.15
369.65
313.15
377.59
323.15

0.982
1.124
1.402
1.043
1.1864
1.437
2.367
2.669
2.287
1.833

2.985
3.642
3.731
4.232
2.990
3.193
3.078
3.068
3.082
2.654

433.91
309.90
263.70
354.65
160.84
199.73
174.07
184.12
171.13
165.80

1195.20
2320.77
2616.50
2375.26

0.038
0.019
0.016
0.020

parameters but the correlation was not satisfactory. It should

be noted, however that we used the LennardJones potential
for the dispersion term [19] and with the use of parameters
obtained from the fitting of the experimental data of vapour
liquid phase equilibria of these chemicals the correlation was
satisfactory. Table 2 provides a comparison of the SAFT parameters. As noted earlier by Voutsas et al. [13], the correlation of these pure component parameters from vapor pressure
and liquid density data did not result in satisfactory binary
VLE calculations.
A water molecule has two hydrogen atoms and two lone
pairs of electrons that are able to form hydrogen bonds. Here
the four-site model is used for water molecule. Each hydroxyl
on the alcohol molecule has one hydrogen and two lone pairs
of electrons that are able to form hydrogen bonds. Here a
two-site model is used for each hydroxyl on the alcohol.
In the case of mixtures, the SAFT equation uses van der
Waals one-fluid mixing rules with the binary interaction parameter, kij , for the dispersion interactions and the parameter,
kijAB , for the associating interactions. These parameters are
fitted to binary VLE data.

4. Phase equilibria of binary mixtures

Using the mixing rules of Eqs. (2) and (3) and Eqs. (4) and
(5), the binary interaction parameters for the 18 binary mixtures are estimated by fitting their vaporliquid equilibrium
data. The results are shown in Table 3. Fig. 1 shows the results
for water/methane at 523.15 K. Fig. 2 presents composition
diagrams for water/propane at 369.65427.59 K. Only the
data at 369.65 were used for parameter estimation. Using the

Fig. 1. Vaporliquid equilibrium for the methane(1)/water(2) mixture at

523.15 K.

binary parameters obtained from the fitting of these data, we

employed the SAFT to predict equilibrium at the other temperatures. As seen from Table 4 and Fig. 2, the agreement
between data and predicted values is excellent. The phase
diagrams for water/ethane, water/butane, water/CO2 and water/propylene systems are not shown but were found to be in
equally good agreement with the data.
As seen in Fig. 3, the calculations are in good agreement
with the data for the propylene/ethanol system. The fitted
and predicted results for other n-alkane/alcohol systems are
not shown but they were also satisfactory as is also indicated
from the root mean square deviations given in Tables 3 and 4.

Table 2
Comparison of the segment parameters of the pure compounds obtained form fitting mixture data in this work with those given by Huang and Radosz [5]
Compound

CH4
C2 H6
C3 H8
C4 H10
C3 H6
CO2

(1010 m)

/k (K)

This work

Reference [5]

This work

Reference [5]

This work

Reference [5]

1.186
1.437
2.367
2.669
2.287
1.833

1.000
1.941
2.696
3.458
2.223
1.417

2.990
3.193
3.078
3.068
3.082
2.654

3.701
3.239
3.162
3.093
3.325
3.171

160.84
199.73
174.07
184.12
171.13
165.80

190.29
191.44
193.03
195.11
213.90
216.08

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X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

Table 3
Estimated binary interaction parameters from regression of binary VLE experimental data
Systems

T (K)

kij

kijAB

RMSD (y)a

RMSD (P)b (%)

Data source

Methane (1) + water (2)

523
0.0291
0.0348
7.8
[22]
Ethane (1) + water (2)
523.15
0.0068
0.0775
9.4
[23]
Propane (1) + water (2)
369.65
0.0571
0.0122
4.5
[24]
Butane (1) + water (2)
313.15
0.0521
2.7
[25]
Propylene (1) + water (2)
377.59
0.1116
0.0059
7.9
[26]
CO2 (1) + water (2)
323.15
0.0452
0.0052
5.1
[27]
Methane (1) + methanol (2)
303.2
0.2204
12.2
[28]
Ethane (1) + methanol (2)
298.15
0.0641
0.0110
21.5
[29]
CO2 (1) + methanol (2)
313.14
0.2025
0.0068
9.5
[30]
Ethane (1) + ethanol (2)
313.40
0.1941
0.0128
8.0
[31]
Propane (1) + ethanol (2)
375.10
0.1687
0.0532
4.8
[32]
Butane (1) + ethanol (2)
345.65
0.1339
0.0074
15.7
[33]
Propylene(1)+ethanol (2)
353.10
0.1405
0.0159
4.2
[34]
Methane (1) + EG (2)
303.2
0.5156
15.3
[28]
Ethane (1) + EG (2)
303.2
0.3326
14.4
[28]
Methanol (1) + water (2)
313.05
0.1043
0.0456
2.8
[35]
Ethanol (1) + water (2)
347.94
0.1182
0.0212
5.1
[35]
EG (1) + water (2)
371.15
0.0525
0.0673
0.0276
5.7
[36]


N
exp 2
cal
a RMSD (y) =
yi ) /(N 1), root mean square deviation of component 1.
i=1 (y

i
N
exp
exp 2
cal
b RMSD (P) (%) = 100
i=1 ((Pi Pi )/Pi ) /(N 1), root mean square deviation for system pressures. N = number of experimental points.
Table 4
Predicted VLE results for binary mixtures
Systems

T (K)

RMSD (y)a

Propane (1) + water (2)

377.59
394.26
410.93
427.59

0.0141
0.0216
0.0310
0.0412

4.1
3.8
4.0
6.5

[24]

Butane (1) + water (2)

298.15
343.15

0.0453
0.0260

4.9
19.9

[25]

Propylene (1) + water (2)

344.26
410.93

0.0036
0.0172

23.5
14.4

[26]

CO2 (1) + water (2)

348.15

0.0058

13.2

[27]

Methane (1) + methanol (2)

283.2
293.2

18.2
14.5

[28]

Ethane (1) + methanol (2)

283.2
293.2
303.2

32.0
26.3
21.3

[28]

Propane (1) + ethanol (2)

350.10
325.10

0.0221
0.0176

14.6
12.2

[32]

Butane (1) + ethanol (2)

323.75
298.45

0.0082
0.0090

19.9
20.7

[33]

Propylene (1) + ethanol (2)

333.10

0.0121

12.2

[34]

CO2 (1) + methanol (2)

308.15
303.18
298.16
291.15

0.0064
0.0068
0.0067
0.0056

8.8
10.8
8.6
14.2

[30]

Methane (1) + EG (2)

283.2
293.2

19.0
16.3

[28]

Ethane (1) + EG (2)

283.2
293.2

8.6
6.2

[28]

a

RMSD

RMSD

(y) =

N

exp 2

RMSD (P)b (%)

(yical yi ) /(N 1), root mean square deviation of component 1.

N
exp
exp 2
cal
(P) (%) = 100
i=1 ((Pi Pi )/Pi ) /(N 1), root mean square deviation for system pressures.
i=1

Data source

X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

Fig. 2. Vaporliquid equilibrium for the propane(1)/water(2) mixture at the

different temperatures.

Fig. 4 shows the calculated results for the water/EG system at 371.15 K. As seen, it exhibits a good agreement between data and calculated values. Table 4 presents VLE calculations for the water/ethanol and water/methanol mixtures
in which a good agreement between data and computed values is also obtained.

5. Phase equilibria of ternary mixtures

The vaporliquid phase equilibria of the ternary mixtures
can be predicted by using the binary interaction parameters of the constituent binary subsystems and the molecular
parameters of the pure components. Nine ternary systems

Fig. 3. Vaporliquid equilibrium for propylene(1)/ethanol(2) mixture at the

different temperatures.

115

Fig. 4. Vaporliquid equilibrium for the ethylene glycol(1)/water(2) mixture

at 371.15 K.

were considered. Tables 5 and 6 summarize the predicted

results.
5.1. Water/ethanol/ethane
Fig. 5 shows the ethanol loadings in supercritical ethane
at 323.15 K and 5 MPa. It can be seen that the SAFT underpredicted the ethanol loading. However the deviations can be
considered acceptable. The ethanol solubility in the supercritical phase is low, and hence calculations were also performed
at 313.15 K and 5 MPa and similar results were obtained.
5.2. Water/ethanol/propane
Fig. 6 shows the relative volatility predictions of ethanol
with respect to propane as a function of the propane concen-

Fig. 5. Ethanol loading in supercritical ethane for the water(1)/ethanol

(2)/ethane(3)mixture at 323.15 K and 5 MPa, S = (yC2 H5 OH /yethane ).

116

X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

Table 5
Predicted VLE results for ternary mixtures
Systems

T (K)

P (MPa)

RMSD (y)a
y1

y2

RMSD (P)b (%)

Data source

Water (1) + ethanol (2) + ethane (3)

313.15
323.15

5.0
5.0

0.0067
0.0038

0.0097
0.0079

34.5
35.7

[37]

Water (1) + ethanol (2) + propane (3)

333.0
363.0
383.0

1.12.0
1.13.7
1.14.1

0.0054
0.0099
0.0153

0.0084
0.0139
0.0259

10.0
5.8
8.6

[38]

Water (1) + ethanol (2) + butane (3)

353.2

0.671.1

0.0208

0.0185

15.2

[38]

Water (1) + ethanol (2) + propylene (3)

333.2

1.82.5

0.0052

0.0089

13.8

[38]

Water (1) + methanol (2) + CO2 (3)

313.15
308.15
303.15
298.15

7.0
6.011.0
7.0
5.07.0

0.0011
0.0033
0.0011
0.0011

0.0031
0.0159
0.0036
0.0017

16.2
6.5
13.7
6.8

[39]
[40]
[40]
[40]

a

RMSD

RMSD

(y) =

N

exp 2

(yical yi ) /(N 1), root mean square deviation of component 1or 2.

N
exp
exp 2
cal
(P) (%) = 100
i=1 ((Pi Pi )/Pi ) /(N 1), root mean square deviation for system pressures.
i=1

Fig. 6. Vaporliquid equilibrium for the water (1)/ethanol (2)/propane (3)

mixture at 383 K. Relative volatility of ethanol to propane; xethanol

(ethanol
weight fraction in the aqueous phase (propane free basis)) = 0.95.

tration in the liquid phase at 383 K. As seen, there is good

agreement between the experimental results and predicted
values. Similar results were obtained at 333 and 363 K.
5.3. Water/ethanol/butane
Fig. 7 shows the relative volatility predictions of ethanol
to butane at 353 K. As seen from the figure the predictions
are quite satisfactory for this system too.

Fig. 7. Vaporliquid equilibrium for the water (1)/ethanol (2)/butane (3)

mixture at 353 K. Relative volatility of ethanol to butane; xethanol

(ethanol
weight fraction in the aqueous phase (butane free basis)) = 0.95.

5.5. Water/methanol/carbon dioxide

Fig. 9 shows the methanol loading in carbon dioxide at
the near critical condition (313.15 K and 7 MPa). As seen the
predictions compare very well with the experimental data at
these low water and methanol vapor concentrations. Predictions at other temperatures and pressures were also carried
out and the root mean square deviations are reported in Table
5. The results are equally satisfactory.
5.6. Other ternary systems

5.4. Water/ethanol/propylene
High-pressure vaporliquid equilibrium for the ternary
system at 333.2 K is shown Fig. 8. The predictions compare
very well with the experimental data.

The predictions of the vaporliquid phase equilibria for other four systems, water/methanol/methane,
water/methanol/ethane, water/ethylene glycol/methane and
water/ethylene glycol/ethane, were also made and given. We

X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

117

Table 6
Predicted VLE results for ternary mixtures at two alcohol liquid phase compositions
Systems

T (K)

P (MPa)

RMSD (y)

RMSD (P) (%)

y1

x2

y2

80a

wt.%

Data source
x2

60a

wt.%

Water (1) + methanol (2) + methane (3)

303.2
293.2
283.2

5.0540.05
5.0540.05
5.0540.05

24.87
24.04
28.99

68.1
59.7
66.6

[28]

Water (1) + methanol (2) + ethane (3)

303.2
293.2
283.2

0.54.0
0.53.0
0.53.0

11.78
8.15
9.38

30.8
29.7
36.5

[28]

Water (1) + EG (2) + methane (3)

303.2
293.2
283.2
303.2

5.0540.06
5.0540.05
5.0540.06
0.54.0

38.84
15.55
16.43
24.23

30.0
16.8
15.5
19.1

[28]

293.2
283.2

0.53.0
0.53.0

17.62
14.19

17.1
15.4

Water (1) + EG (2) + ethane (3)

[28]

Weight % of component 2 in the aqueous phase (hydrocarbon free basis).

Fig. 8. Vaporliquid equilibrium for the water (1)/ethanol (2)/propylene

(3) mixture at 333.2 K. Relative volatility of ethanol to propylene; xethanol

(ethanol weight fraction in the aqueous phase (propylene free basis)) = 0.95.

only compared the predicted pressure values with the experimental data, because the experimental data of vapor phase
composition for these ternary systems were unavailable from
literature. The agreement was satisfactory except ones at
x2 = 60 wt.% for water/methanol/methane as indicated in
Table 6 from the root mean square deviation values.

6. Conclusions
The SAFT equation of state is employed to predict the
phase equilibria for nine hydrocarbon/alcohol/water ternary
systems. Binary interaction parameters estimated from the
vaporliquid equilibrium data of the constituent binary subsystems were employed. A satisfactory agreement between
predicted values and experimental data was found except for

Fig. 9. Methanol loading in supercritical carbon dioxide for the water

(1) /methanol (2) /carbon dioxide (3) mixture at 313.15 K and 7 MPa.
S = (yCH3 OH /yCO2 ).

the water/methanol/methane system at the low methanol concentration in the liquid phase (60 wt.%).
List of symbols
A
Helmholtz free energy (J)
d
hard-sphere diameter (1 1010 m)
g
radius distribution function
k
Boltzmann constant (J K1 )
m
effective number of segments
M
number of associate sites
N
number of molecules
NA
Avogadro constant (6.02217 1023 mol1 )
R
gas constant (8.3143 J mol1 K1 )
S
ethanol loading in supercritical phase
T
absolute temperature (K)
x
mole fraction in liquid phase
xi
mole fraction of component i

118

X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111118

xethanol
ethanol weight fraction in the aqueous phase (hydrocarbon free basis)
XiA
mole fraction of molecule i not bonded at site A
y
mole fraction in vapor phase
Z
compressibility factor

Greek letters

1/kT
/k
energy parameter of dispersion (K)
AB /k energy parameter of association between sites A and
B (K)
AB
bonding volume
AB
association strength between sites A and B

chemical potential

molar density (mol/m3 )

n
number density (m3 )

soft-sphere diameter (1 1010 m)

Subscripts
i, j, k components
Superscripts
assoc association interaction
chain hard-sphere chain
disp
dispersion interaction
hs
hard-sphere
A,
B association site
res
residual term

Acknowledgements
The financial support from National Science and Engineering Research Council of Canada (NSERC) is greatly appreciated.
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