Fluid Phase Equilibria 224 (2004) 111–118

Vapor–liquid 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 vapor–liquid equilib-
rium (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 diox-
ide and finally EG with methane and ethane. Moreover, vapor–liquid 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, wa-
ter/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 60–68% when the methanol
concentration in the liquid phase was 60 wt.%.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Vapor–liquid equilibrium; SAFT; Alcohol; Alkane; Water

1. Introduction wide variety of the thermodynamic properties and phase equi-

The modeling of phase behavior and the calculation of
thermodynamic properties of aqueous solutions involving al-
cohols, hydrocarbon, water and carbon dioxide is of con-
siderable industrial importance. For example, such informa-
tion 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 in-
hibition 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 asso-
ciating fluid theory (SAFT), which is based on Wertheim’s
first-order thermodynamic perturbation theory for associat-
ing 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).
libria for industrially important fluids [9]. Huang and Radosz
[6] applied the original SAFT to calculate the phase equilib-
ria of water/n-alkane, water/methane and water/ethane, and
hydrocarbon/alcohol mixtures. It is noted that for the wa-
ter/methane and water/ethane systems they only calculated
the solubility of water in the hydrocarbon-rich phase. Kraska
and Gubbins [10] proposed the Lennard–Jones (LJ)-SAFT,
in which the chain segments were treated as Lennard–Jones
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 crit-
ical behaviour of n-alkane/water mixtures, and good agree-
ment 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

0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.06.052
112 X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111–118
and n-decylpentaoxyethylene ether. In additon, Voutsas et
al. [13] compared the original SAFT with the Cubic-Plus-
Association Equation of State (CPA EoS) for the phase equi-
libria 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 sat-
isfactorily 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 equa-
tion to model the phase equilibria of the ternary sys-
tems, water/alcohol/alcohol, and the constituent subsys-
tems [15]. In this work, we applied the above SAFT
for the correlation and prediction of Vapor–liquid equilib-
ria of binary mixtures of alcohols with n-alkanes, propy-
lene, water and carbon dioxide. Furthermore, we em-
ployed the SAFT to predict high pressure VLE in ternary
systems, water/ethanol/n-alkane (ethane, propane and bu-
tane), water/ethanol/propylene, water/methanol/carbon diox-
ide, water/methanol/methane, water/methanol/ethane, wa-
ter/EG/methane and water/EG/ethane. It is noted that there
are no other applications of SAFT to VLE of the wa-
ter/alcohol/hydrocarbon ternary mixtures. However, ternary
LLE calculations were done for the water–ethanol–benzene
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 seg-
ment 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, dis-
persion and association terms as follows
Ares = A − Aid = Ahs + Achain + Adisp + Aassoc
where Aid is the free energy of an ideal gas with the same
density and temperature as the system, Ahs the free ene-
rgy of a hard-sphere fluid relative to the idea gas. The
Ahs term is calculated with the Boublik–Mansoori–
Carnahan–Starling–Leland equation [17,18] and the
Barker–Henderson 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 Lennard–Jones potential
[19]. The following combining rules are used for the cross
parameters between different segments, ␴ij and ␧ij
σii + σjj
σij = (2)
2
√
εij = (1 − kij ) εii εjj (3)
where σ ii or ␴jj is the soft-sphere diameter of segment i or
j, ␧ii or ␧jj is the energy parameter of the L–J 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]:
κAi Bi + κAj Bj
κAj Bi = κAi Bj = (4)
2


εAj Bi = εAi Bj = (1 − kijAB ) (εAi Bi εAj Bj ) (5)
where κAB is the bonding volume and εAB /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 pa-
rameters for non-associating fluids and five parameters for
associating fluids. These parameters are the Lennard–Jones
(L–J) potential well depth (ε/k), the soft sphere diameter of
segments (σ), the number of segments of the molecule (m),
the bonding volume (κAB ) and the association energy be-
tween sites A and B (εAB ). These parameters can be estimated
from the regression of saturated vapor pressure and liquid
density data. In this work, the segment parameters (ε/k, σ, m,
κAB , εAB ) for water, ethanol, methanol, EG, methane, ethane,
propane, butane, propylene, and carbon dioxide need to be
obtained for the correlation and prediction of the correspond-
ing binary and ternary mixtures. The parameters for water,
methanol, ethanol, EG and were obtained by simultaneously
(1) 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 pa-
rameters 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 poten-
tial one for the dispersion term [5,6]. We used their reported
 X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111–118 113

Table 1
Estimated segment parameters for pure fluids
Fluid T (K) m σ (10−10 m) ε/k (k) εAB /k (K) κAB
Water 283–483 0.982 2.985 433.91 1195.20 0.038
Methanol 295–489 1.124 3.642 309.90 2320.77 0.019
Ethanol 303–503 1.402 3.731 263.70 2616.50 0.016
EG 375–496 1.043 4.232 354.65 2375.26 0.020
Methane 523 1.1864 2.990 160.84
Ethane 523.15 1.437 3.193 199.73
Propane 369.65 2.367 3.078 174.07
Butane 313.15 2.669 3.068 184.12
Propylene 377.59 2.287 3.082 171.13
CO2 323.15 1.833 2.654 165.80

parameters but the correlation was not satisfactory. It should

be noted, however that we used the Lennard–Jones 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 pa-
rameters. As noted earlier by Voutsas et al. [13], the correla-
tion 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 pa-
Fig. 1. Vapor–liquid equilibrium for the methane(1)/water(2) mixture at
rameter, kij , for the dispersion interactions and the parameter,
523.15 K.
kijAB , for the associating interactions. These parameters are
fitted to binary VLE data. binary parameters obtained from the fitting of these data, we
employed the SAFT to predict equilibrium at the other tem-
peratures. As seen from Table 4 and Fig. 2, the agreement
4. Phase equilibria of binary mixtures between data and predicted values is excellent. The phase
diagrams for water/ethane, water/butane, water/CO2 and wa-
Using the mixing rules of Eqs. (2) and (3) and Eqs. (4) and ter/propylene systems are not shown but were found to be in
(5), the binary interaction parameters for the 18 binary mix- equally good agreement with the data.
tures are estimated by fitting their vapor–liquid equilibrium As seen in Fig. 3, the calculations are in good agreement
data. The results are shown in Table 3. Fig. 1 shows the results with the data for the propylene/ethanol system. The fitted
for water/methane at 523.15 K. Fig. 2 presents composition and predicted results for other n-alkane/alcohol systems are
diagrams for water/propane at 369.65–427.59 K. Only the not shown but they were also satisfactory as is also indicated
data at 369.65 were used for parameter estimation. Using the 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 m σ (10−10 m) ε/k (K)

This work Reference [5] This work Reference [5] This work Reference [5]
CH4 1.186 1.000 2.990 3.701 160.84 190.29
C2 H6 1.437 1.941 3.193 3.239 199.73 191.44
C3 H8 2.367 2.696 3.078 3.162 174.07 193.03
C4 H10 2.669 3.458 3.068 3.093 184.12 195.11
C3 H6 2.287 2.223 3.082 3.325 171.13 213.90
CO2 1.833 1.417 2.654 3.171 165.80 216.08
114 X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111–118

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]


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

i
b RMSD (P) (%) = 100
N exp exp 2
i=1 ((Pi − Pi )/Pi ) /(N − 1), root mean square deviation for system pressures. N = number of experimental points.
cal

Table 4
Predicted VLE results for binary mixtures
Systems T (K) RMSD (y)a RMSD (P)b (%) Data source
Propane (1) + water (2) 377.59 0.0141 4.1 [24]
394.26 0.0216 3.8
410.93 0.0310 4.0
427.59 0.0412 6.5
Butane (1) + water (2) 298.15 0.0453 4.9 [25]
343.15 0.0260 19.9
Propylene (1) + water (2) 344.26 0.0036 23.5 [26]
410.93 0.0172 14.4
CO2 (1) + water (2) 348.15 0.0058 13.2 [27]
Methane (1) + methanol (2) 283.2 18.2 [28]
293.2 14.5
Ethane (1) + methanol (2) 283.2 32.0 [28]
293.2 26.3
303.2 21.3
Propane (1) + ethanol (2) 350.10 0.0221 14.6 [32]
325.10 0.0176 12.2
Butane (1) + ethanol (2) 323.75 0.0082 19.9 [33]
298.45 0.0090 20.7
Propylene (1) + ethanol (2) 333.10 0.0121 12.2 [34]
CO2 (1) + methanol (2) 308.15 0.0064 8.8 [30]
303.18 0.0068 10.8
298.16 0.0067 8.6
291.15 0.0056 14.2
Methane (1) + EG (2) 283.2 19.0 [28]
293.2 16.3
Ethane (1) + EG (2) 283.2 8.6 [28]
293.2 6.2


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


N exp exp 2
b RMSD (P) (%) = 100 i=1 ((Pi − Pi )/Pi ) /(N − 1), root mean square deviation for system pressures.
cal
 X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111–118
Fig. 2. Vapor–liquid equilibrium for the propane(1)/water(2) mixture at the
different temperatures.
Fig. 4 shows the calculated results for the water/EG sys-
tem at 371.15 K. As seen, it exhibits a good agreement be-
tween data and calculated values. Table 4 presents VLE cal-
culations for the water/ethanol and water/methanol mixtures
in which a good agreement between data and computed val-
ues is also obtained.
5. Phase equilibria of ternary mixtures
The vapor–liquid phase equilibria of the ternary mixtures
can be predicted by using the binary interaction parame-
ters of the constituent binary subsystems and the molecular
parameters of the pure components. Nine ternary systems
Fig. 3. Vapor–liquid equilibrium for propylene(1)/ethanol(2) mixture at the
different temperatures.
115
Fig. 4. Vapor–liquid 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 under-
predicted the ethanol loading. However the deviations can be
considered acceptable. The ethanol solubility in the supercrit-
ical 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) 111–118

Table 5
Predicted VLE results for ternary mixtures
Systems T (K) P (MPa) RMSD (y)a RMSD (P)b (%) Data source
y1 y2
Water (1) + ethanol (2) + ethane (3) 313.15 5.0 0.0067 0.0097 34.5 [37]
323.15 5.0 0.0038 0.0079 35.7
Water (1) + ethanol (2) + propane (3) 333.0 1.1–2.0 0.0054 0.0084 10.0 [38]
363.0 1.1–3.7 0.0099 0.0139 5.8
383.0 1.1–4.1 0.0153 0.0259 8.6
Water (1) + ethanol (2) + butane (3) 353.2 0.67–1.1 0.0208 0.0185 15.2 [38]
Water (1) + ethanol (2) + propylene (3) 333.2 1.8–2.5 0.0052 0.0089 13.8 [38]
Water (1) + methanol (2) + CO2 (3) 313.15 7.0 0.0011 0.0031 16.2 [39]
308.15 6.0–11.0 0.0033 0.0159 6.5 [40]
303.15 7.0 0.0011 0.0036 13.7 [40]
298.15 5.0–7.0 0.0011 0.0017 6.8 [40]


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


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

Fig. 7. Vapor–liquid equilibrium for the water (1)/ethanol (2)/butane (3)

Fig. 6. Vapor–liquid equilibrium for the water (1)/ethanol (2)/propane (3)
∗ mixture at 353 K. Relative volatility of ethanol to butane; xethanol (ethanol
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.
5.4. Water/ethanol/propylene
High-pressure vapor–liquid equilibrium for the ternary
system at 333.2 K is shown Fig. 8. The predictions compare
very well with the experimental data.
∗
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. Predic-
tions 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
The predictions of the vapor–liquid phase equi-
libria 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) 111–118 117

Table 6
Predicted VLE results for ternary mixtures at two alcohol liquid phase compositions
Systems T (K) P (MPa) RMSD (y) RMSD (P) (%) Data source

y1 y2 x2∗ = 80a wt.% x2∗ = 60a wt.%

Water (1) + methanol (2) + methane (3) 303.2 5.05–40.05 24.87 68.1 [28]
293.2 5.05–40.05 24.04 59.7
283.2 5.05–40.05 28.99 66.6
Water (1) + methanol (2) + ethane (3) 303.2 0.5–4.0 11.78 30.8 [28]
293.2 0.5–3.0 8.15 29.7
283.2 0.5–3.0 9.38 36.5
Water (1) + EG (2) + methane (3) 303.2 5.05–40.06 38.84 30.0 [28]
293.2 5.05–40.05 15.55 16.8
283.2 5.05–40.06 16.43 15.5
Water (1) + EG (2) + ethane (3) 303.2 0.5–4.0 24.23 19.1 [28]
293.2 0.5–3.0 17.62 17.1
283.2 0.5–3.0 14.19 15.4
a Weight % of component 2 in the aqueous phase (hydrocarbon free basis).

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

Fig. 8. Vapor–liquid equilibrium for the water (1)/ethanol (2)/propylene (1) /methanol (2) /carbon dioxide (3) mixture at 313.15 K and 7 MPa.
∗
(3) mixture at 333.2 K. Relative volatility of ethanol to propylene; xethanol S = (yCH3 OH /yCO2 ).
(ethanol weight fraction in the aqueous phase (propylene free basis)) = 0.95.
the water/methanol/methane system at the low methanol con-
only compared the predicted pressure values with the exper- centration in the liquid phase (60 wt.%).
imental data, because the experimental data of vapor phase
composition for these ternary systems were unavailable from List of symbols
literature. The agreement was satisfactory except ones at A Helmholtz free energy (J)
x2∗ = 60 wt.% for water/methanol/methane as indicated in d hard-sphere diameter (1 × 10−10 m)
Table 6 from the root mean square deviation values. g radius distribution function
k Boltzmann constant (J K−1 )
m effective number of segments
6. Conclusions M number of associate sites
N number of molecules
The SAFT equation of state is employed to predict the NA Avogadro constant (6.02217 × 1023 mol−1 )
phase equilibria for nine hydrocarbon/alcohol/water ternary R gas constant (8.3143 J mol−1 K−1 )
systems. Binary interaction parameters estimated from the S ethanol loading in supercritical phase
vapor–liquid equilibrium data of the constituent binary sub- T absolute temperature (K)
systems were employed. A satisfactory agreement between x mole fraction in liquid phase
predicted values and experimental data was found except for xi mole fraction of component i
118 X.-S. Li, P. Englezos / Fluid Phase Equilibria 224 (2004) 111–118

∗
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