Ind. Eng. Chem. Res.

2008, 47, 3247-3252 3247

Prediction of Partition Coefficients of Benzothiophene and Benzothiophene

1,1-Dioxide in Octane/Acetonitrile System Using COSMO Theory
Yusuke Shimoyama,*,† Yoshio Iwai,† Satoshi Yoda,‡ and Takeshi Furuya‡
Department of Chemical Engineering, Faculty of Engineering, Kyushu UniVersity 744 Motooka Nishi-ku,
Fukuoka 819-0395, Japan, and Nanotechnology Research Institute, National Institute of AdVanced Industrial
Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan

The partition coefficients of benzothiophene (BT) and benzothiophene 1,1-dioxide (BTDO) in the octane/
acetonitrile system were predicted using the COSMO (conductor-like screening model) based activity coefficient
models COSMO-SAC (segment activity coefficient) and COSMO-UNIQUAC. In COSMO-UNIQUAC, a
segment activity coefficient was described in a UNIQUAC-type equation. The results with COSMO-UNIQUAC
were compared with those from the COSMO-SAC model. It was found that COSMO-UNIQUAC reproduced
the experimental data more accurately than COSMO-SAC. The surface charge density profiles (σ-profiles)
of functional groups on BT and BTDO molecules were utilized to determine that the partition coefficients of
BTDO are much lower than those of BT. A hypothetical molecule with the volume and surface area of
BTDO was conducted by using the σ-profiles of functional groups on BT and BTDO. The partition coefficients
of the hypothetical component were predicted by COSMO-UNIQUAC. It was revealed that the partitions of
BTDO in the octane/acetonitrile system were influenced from the charge density changes by the oxidation on
not only the sulfur atom but also on the carbon and hydrogen atoms.

1. Introduction to predict vapor-liquid equilibria,14-16 solubilities,17 and high

Novel desulfurization processes are required to reduce the
sulfur content in gasoline and diesel fuel to extremely low levels.
In oxidative desulfurization, thiophene, benzothiophene, and
their derivatives can be transformed into sulfones and sulfoxides.
These oxidative compounds are extracted easily with polar
solvents. A recent paper has stated that oxidative desulfurizations
are capable of reducing the sulfur contents in fuel oil to lower
levels.1 Recently, oxidative desulfurization processes with fuel
oil/acetonitrile biphasic systems have been proposed.2-4 In these
processes, benzothiophenes and their derivatives are extracted
into the acetonitrile phase and oxidized effectively.
It is very important for the oxidative desulfurization process
design to recognize the liquid-liquid equilibria for fuel oil/
acetonitrile systems and the partitions of the sulfur compounds
and their oxides in fuel oil/acetonitrile biphasic systems as
fundamental knowledge. Furuya et al.5,6 have reported experi-
mental data of the liquid-liquid equilibria for acetonitrile +
octane, + decane, and + hexadecane systems. The partition
coefficients of benzothiophene and benzothiophene 1,1-dioxide
in the octane/acetonitrile system have been also measured at
298-343 K.5 In addition to these measurements, the correlations
or predictions can be a highly useful tool for the design and
development of oxidative desulfurization processes.
Activity coefficient models, such as NRTL,7 UNIQUAC,8
ASOG,9 and UNIFAC10 models, have been utilized to correlate
the liquid-liquid equilibria and the partition coefficients.
However, many parameters determined by data fitting are
required in these models, especially for multicomponent systems.
Based on quantum calculations with the conductor-like screening
model (COSMO),11 COSMO for real solvents (COSMO-RS)12
and COSMO segment activity coefficient (COSMO-SAC)13
models have been developed to predict the activity coefficients
in mixtures without data fitting. These models have been utilized
†
‡
Kyushu University.
AIST.
pressure phase equilibria18-20 until now. From the literature, it
has been verified that the COSMO-based models can be very
useful to predict the thermodynamic properties of fluids and
their mixtures.
In this work, the partition coefficients of benzothiophene (BT)
and benzothiophene 1,1-dioxide (BTDO) in the octane/aceto-
nitrile system were predicted by using the COSMO-based
models COSMO-SAC and COSMO-UNIQUAC. In COSMO-
UNIQUAC, the segment activity coefficients are described with
the UNIQUAC equation8 as proved by Lin and Sandler.13
Furthermore, the surface charge density profile (σ-profile) on
the functional groups of BT and BTDO molecules were used
for the discussions about the partitions of BTDO in the octane/
acetonitrile system being much lower than those of BT. A
hypothetical molecule with the volume and surface area of a
BTDO molecule was constructed by using the σ-profiles on the
functional groups of BT and BTDO. The predictions of partition
coefficients of the hypothetical component were carried out by
COSMO-UNIQUAC. These results were compared with those
of BT and BTDO.
2. Definition of Partition Coefficient
In this work, it was assumed that the concentrations of BT
or BTDO in octane- or acetonitrile-rich phase were in infinite
dilution conditions, because the experimental data5 used for the
comparisons with the predictions had been obtained in very
small concentrations of BT or BTDO, with 80 ppm (weight
basis) as a sulfur concentration in total of those in octane- and
acetonitrile-rich phases. The partition coefficient of BT or BTDO
in the octane/acetonitrile system based on mole fractions Ki is
given from the relationship of liquid-liquid equilibria by the
following equation.
xIi γIIi
Ki ) ) (1)
xIIi γIi

10.1021/ie071377h CCC: $40.75 © 2008 American Chemical Society

Published on Web 04/05/2008
3248 Ind. Eng. Chem. Res., Vol. 47, No. 9, 2008

where xi and γi are the mole fraction and activity coefficient of The segment activity coefficient is calculated from the
the component i, respectively. The superscripts “I” and “II” σ-profile in the mixture and the exchange energy of the segment
mean octane- and acetonitrile-rich phases, respectively. The pair described as follows.

{ [ ]}
partition coefficient based on the weight fraction Ki,w can be
obtained from that based on the mole fraction as follows. -∆W(σm,σn)
1n Γ(σm) ) -1n ∑
( ) ( )
p(σn) Γ(σn) exp (8)
RT
M1xII1 + M2xII2 γIIi M1xII1 + M2xII2 σn

Ki,w ) Ki ) (2)
M1xI1 + M2xI2 γIi M1xI1 + M2xI2 where R is the gas constant. This equation should be solved
iteratively. The activity coefficient of component i in mixture
where M is the molecular weight. The subscripts “1” and “2” γi can be obtained from the segment activity coefficient Γ.
mean octane and acetonitrile. The experimental data of the
Ai
∑
liquid-liquid equilibria in the octane/acetonitrile system5 were
used for the mole fractions of octane and acetonitrile in each
ln γi ) pi(σm)[ln Γ(σm) - ln Γi(σm)] + ln γCi (9)
aeff σ m
phase in eq 2. The activity coefficients in octane- and aceto-

()
nitrile-rich phases were calculated by COSMO-SAC or COSMO- φi θi φi
z
UNIQUAC models as described below. ln γCi ) ln
xi
+
2
qi ln
φi
+ li -
xi
∑j xjlj (10)
3. Activity Coefficient Model

()
z rixi qixi
3.1. COSMO-SAC. The COSMO-SAC method13 is the
li ) (ri - qi) - (ri - 1), θi ) , φi ) (11)
method for predicting thermodynamic properties in mixtures
∑j rjxj ∑j qjxj
2
with a statistical approach by quantum calculations, based on
the COSMO model.11 In the COSMO-SAC method, the predic-
tions of thermodynamic properties are performed by using a where z is the coordination number. r and q are the surface
charge density σ of a segment in a molecular surface obtained area and volume parameters. The superscript “C” means the
from COSMO calculations. In this work, the COSMO calcula- combinatorial contribution from the differences of the molecular
tions were carried out with Gaussian 03W software.21 The size and shapes. In eq 10, the activity coefficients were
probability of finding σ in pure component i, the σ-profile calculated in the infinite dilution condition for BT or BTDO;
pi(σ), is given by the following equation. the mole fractions were set to zero. For the mole fractions of
octane and acetonitrile, the liquid-liquid equilibrium data for
Ai(σ)
pi(σ) ) (3) the octane/acetonitrile system were used. Finally, the partition
Ai coefficient of the solute in the octane/acetonitrile system can
be demonstrated from substituting eq 9 to eq 1.
where Ai(σ) is the total surface area of the segment with charge
density σ, and Ai is the surface area of molecule i. As the BT γIIi Ai
or BTDO concentrations were the infinite dilution conditions, 1n Ki ) ) ∑pi(σm)[1n ΓII(σm) - 1n ΓI(σm)] +
aeff σm
the probability of finding σ in the mixture is obtained from the γIi
probabilities in pure octane and acetonitrile.
i - 1nγi ) (12)
(1nγC,II C,I

x1A1p1(σ) + x2A2p2(σ)
p(σ) ) (4) 3.2. COSMO-UNIQUAC. Lin and Sandler13 have explained
x1A1 + x2A2 the relationship of the segment activity coefficient from the
UNIQUAC equation.8 The interaction energy between the
The subscripts “1” and “2” denote octane and acetonitrile, surface charge segments σm and σn is explained with the misfit
respectively. The surface charge density σ was also used for energy and hydrogen bonding interaction described by eqs 5
the calculations of the segment pair energies contributed from and 6.
the misfit energy Emf and the hydrogen bonding interaction Ehb
given as follows. U(σm,σn) ) [Emf(σm,σn) - Emf(σm,0) - Emf(σn,0)] +
[Ehb(σm,σn) - Ehb(σm,0) - Ehb(σn,0)] (13)
(0.64)(0.3)a3/2
eff
Emf(σm,σn) ) (σm + σn) (5) In the UNIQUAC formula, the activity coefficient of the
20
surface charge segment in mixture can be demonstrated by the
Ehb(σm,σn) ) chb max[0,σac-σhb] min[0,σdo+σhb] (6) following expression.

p(σn)τmn
where aeff and 0 are the standard segment surface area and the
permittivity of free space with 0 ) 5.724 × 10-8 (e2 mol J-1
1n Γ(σm) ) 1 - 1n ∑ p(σn)τnm - ∑ (14)
Å-1), respectively. chb and σhb are the constant and the cutoff
σ n σ
∑
σ
p(σk)τkn
n

value for the hydrogen bonding interactions, respectively. σac k

[ ]
and σdo mean the larger and smaller values of σm and σn. From U(σm,σn) - U(σn,σn)
these interaction energies, the exchange energy required to form τmn ) exp -
the segment pair of σm and σn from a neutral pair is obtained 2RT
by the following equation. The activity coefficients and the partition coefficients of
component i are calculated from eqs 9 and 12 as in the case of
∆W(σm,σn) ) Emf(σm,σn) + Ehb(σm,σn) (7) the COSMO-SAC model.
 Ind. Eng. Chem. Res., Vol. 47, No. 9, 2008 3249

Table 1. Parameters in COSMO-SAC and COSMO-UNIQUAC

chb × 10-5
method ref aeff [Å2] σhb [e/Å2] [kJ mol-1 Å4 e-2]
COSMO-SAC 13 7.50 0.0084 3.581
COSMO-SAC this work 7.50 0.0082 6.268
COSMO-UNIQUAC this work 7.50 0.0082 2.501

Table 2. Deviations between Experimental and Predicted Results of

Partition Coefficient of Benzothiophene (BT) and Benzothiophene
1,1-Dioxide (BTDO) in Octane/Acetonitrile System
δ × 102
sulfur component N COSMO-SAC COSMO-UNIQUAC
BT 6 1.4 1.2
BTDO 6 0.24 0.12
Figure 1. Partition coefficients of benzothiophene (BT) and benzothiophene
δ ) (1/N)∑Nnd)1|Ki,exp
w
- Ki,calc
w
|, where N is the number of data points.
1,1-dioxide (BTDO) in octane/acetonitrile system. Experimental data:5 BT
(O); BTDO (b). Predicted results: COSMO-SAC (s); COSMO-UNIQUAC
3.3. Details of Parameters in COSMO-SAC and COSMO- (---).
UNIQUAC. In the COSMO-SAC and COSMO-UNIQUAC
models, a standard segment surface area aeff, a constant chb, and
a cutoff value σhb for the hydrogen bonding interaction are
needed to calculate the exchange energy in eq 7 and the
interaction energy of a segment pair in eq 13. In this work, the
value of aeff given by Lin and Sandler13 was used in both
COSMO-based models: aeff ) 7.50 Å2. The parameter chb was
determined from fitting the experimental partition coefficient
of BT in the octane/acetonitrile system at 343 K, and the value
was 6.268 × 105 and 2.501 × 105 kJ mol-1 Å4 e-2 in COSMO-
SAC and COSMO-UNIQUAC, respectively. σhb was set to
0.0082 e Å-2 from the literature.22 Table 1 lists the values of
the parameters aeff, chb, and σhb in this work and the literature
by Ling and Sandler.13
The molecular volume and surface area parameters are
Figure 2. Relationship between σ-profile of benzothiophene (BT) and
required for the calculations of the combinatorial contributions segment activity coefficient difference in octane- and acetonitrile-rich phases
of the activity coefficients in eqs 10 and 11. These molecular at 298 K: σ-profile of BT (s); segment activity coefficient difference
parameters are obtained from the following equation. (---).

Vi Ai
ri ) and qi ) (15)
Vst Ast

Vi and Ai are the molecular volume and surface area of molecule

i resulted from COSMO calculations. Vst and Ast denote standard
volume and surface area, respectively. In this work, the volume
and surface area of methane molecule from COSMO calcula-
tions were applied as the standard values. These values are 37.98
Å3 and 56.04 Å2 for the volume and surface area.

4. Results and Discussion

Figure 1 shows the predicted results of the partition coef-
ficients of BT in the octane/acetonitrile system at 298-343 K.
The deviations between the experimental and predicted results
are listed in Table 2. The results with COSMO-SAC and
COSMO-UNIQUAC for BT are in good agreement with the
experimental data. The results for BTDO with COSMO-
UNIQUAC reproduce the experimental data more accurately
than those with COSMO-SAC. These results can be explained
by that the segment activity coefficients are expressed in
consideration of the local area fractions of the segments in the
UNIQUAC formula.
As described in eq 12, the partition coefficients are calculated
from a multiplication of the σ-profile of the solute and the
segment activity coefficient difference in the mixture between
octane- and acetonitrile-rich phases. The relationships between
the σ-profile of the solute and the segment activity coefficient
difference are shown for BT and BTDO in Figures 2 and 3. As
Figure 3. Relationship between σ-profile of benzothiophene 1,1-dioxide
(BTDO) and segment activity coefficient difference in octane- and aceto-
nitrile-rich phases at 298 K: σ-profile of BTDO (s); segment activity
coefficient difference (---).
shown in Figures 2 and 3, the segment activity coefficient
differences decrease considerably in positive and negative charge
densities. The σ-profile of BT has a large peak near zero charge
density. On the other hand, the profiles for BTDO indicate large
values in high positive and negative charge densities. It was
considered that the σ-profile for BTDO results in much lower
values of the partition coefficients of BTDO than those of BT.
BT and BTDO molecules were divided into the functional
groups as given in Figure 4 in order to discuss the changes of
these σ-profiles by the oxidation from BT to BTDO. Figure 5
shows the σ-profiles of the S group on BT and the SO2 group
3250 Ind. Eng. Chem. Res., Vol. 47, No. 9, 2008
Figure 4. Functional groups on (a) benzothiophene and (b) benzothiophene
1,1-dioxide.
Figure 5. σ-profiles of S group on benzothiophene (s) and SO2 group on
benzothiophene 1,1-dioxide (---).
Figure 6. σ-profiles of CH groups on benzothiophene (s) and ben-
zothiophene 1,1-dioxide (---).
on BTDO. The σ-profile of the SO2 group on BTDO shifts to
the right side and has a peak higher than that of the S group on
BT. It is no wonder this σ-profile changes because the SO2 group
on the BTDO molecule is charged more negative due to the
oxidation and the surface area increases due to the addition of
two oxygen atoms. For CH groups on BT and BTDO, the
σ-profiles are given in Figure 6. It is found that the σ-profile of
CH groups for BTDO shifts to the negative region by the
oxidation of BT. The reason is considered to be that the charged
Figure 7. σ-profiles of benzothiophene (s) and hypothetical component
(---).
Figure 8. σ-profiles of benzothiophene 1,1-dioxide (s) and hypothetical
component (---).
molecule due to the oxidation is neutralized by the positive
charge of the CH group.
As shown in Figure 6, the surface charge densities of the
CH group on BTDO are different from those on BT though the
atoms of CH groups on both molecules are identical. It is
considered that the differences of group properties affect the
calculations of partition coefficients of BTDO. In conventional
group contribution methods, ASOG9 and UNIFAC,10 the activity
coefficient can be explained by contributions of groups whose
properties are identical in any molecules. The effects of these
differences of group properties cannot be explained by the group
contribution methods. In this work, a hypothetical BTDO
molecule was utilized to verify the effect of the surface charge
density difference on the calculation of the partition coefficient
of BTDO in the octane/acetonitrile system. The σ-profile of the
hypothetical BTDO molecule was composed of those of the
CH group on BT and the SO2 group on BTDO. This explanation
for the hypothetical BTDO molecule is the same as the case of
the conventional group contribution method. The comparisons
of the partition coefficients between the hypothetical and real
BTDOs are useful to verify the effect of the surface charge
density difference of CH group. The volume and surface area
of BTDO molecule were used as those of the hypothetical
molecule. The surface charge density of the hypothetical
molecule is expressed as follows.
Ahypphyp(σm) ) ACH
BT pBT (σm) + ABTDOpBTDO(σm)
CH SO2 SO2
(16)
where the subscript “hyp” indicates the hypothetical molecule,
and the superscripts mean the functional groups on the molecule.
This σ-profile is compared with those of BT and BTDO in
Figures 7 and 8. As shown Figure 7, the profiles for the
hypothetical molecule are almost the same as those for BT at

Figure 9. Predicted results of partition coefficients of hypothetical
component, benzothiophene (BT), and benzothiophene 1,1-dioxide (BTDO)
in octane/acetonitrile system with COSMO-UNIQUAC. Experimental data:5
BT (O); BTDO (b). Predicted results: hypothetical component (s); BT
(‚‚‚);BTDO (---).
-0.010 to 0.007 e/Å2 contributed from the CH group. In Figure
8, the σ-profiles of the hypothetical and BTDO molecules are
identical to each other at 0.005-0.015 e/Å2 contributed from
the surface charge densities of SO2 groups. At the other charge
densities, the σ-profile of the hypothetical molecule is more
positive than that of BTDO. It corresponds to the σ-profiles of
CH groups on BT and BTDO as shown in Figure 6.
The partition coefficients of the hypothetical component in
the octane/acetonitrile system were predicted with COSMO-
UNIQUAC. The predicted results are compared with those of
BT and BTDO and presented in Figure 9. For the hypothetical
component, the partition coefficients are 0.03-0.1 times lower
than those of BT. The partition coefficients of BTDO are 0.005-
0.04 times lower than those of BT. These results mean that the
partition coefficients of BTDO are influenced by not only the
changes of the charge densities from S to SO2 groups but also
the shift of the σ-profile on the CH group by the oxidation.
COSMO-based models can explain these phenomena in the
consideration of the charge density changes on the molecular
surface by the oxidation. The COSMO-based models are
superior to the conventional group contribution methods, such
as ASOG9 and UNIFAC,10 in which the properties of functional
groups are identical in any molecules, because the consideration
of the changes of the properties of functional groups can be
made in each molecule.
5. Conclusion
The partition coefficients of benzothiophene (BT) and ben-
zothiophene 1,1-dioxide (BTDO) in the octane/acetonitrile two-
phase system were predicted from two COSMO-based models,
COSMO-SAC and COSMO-UNIQUAC. The hydrogen bonding
interaction parameter in both models was determined from fitting
to the experimental data of the partition coefficients of BT at
343.2 K. The predicted results for BTDO with COSMO-
UNIQUAC reproduce the experimental data more accurately
than those with COSMO-SAC.
The σ-profiles of functional groups, CH, S, and SO2, on BT
and BTDO molecules were used to discuss the effect of the
surface charge density changes by the oxidation on the predic-
tions of the partition coefficients of the oxidized BTDO. The
peak of the SO2 σ-profile for BTDO is at a region more positive
than those of the S group on BT due to oxidation. The σ-profile
for the CH group on BTDO shifts to the negative region
compared with that on BT. Furthermore, a hypothetical molecule
Ind. Eng. Chem. Res., Vol. 47, No. 9, 2008 3251
was constructed from the σ-profiles of the CH group on the
BT molecule and of the SO2 group on the BTDO molecule.
The partition coefficients of the hypothetical component in the
octane/acetonitrile system were predicted from COSMO-UNI-
QUAC. From the predicted partition coefficients of BT, BTDO,
and the hypothetical component, it was revealed that the partition
coefficients of BTDO are affected by the changes of the surface
charge densities on CH groups by the oxidation from BT to
BTDO. It is considerable that COSMO-based models can
demonstrate the effect of the surface charge densities on
functional groups which cannot be explained by conventional
group contribution methods including the same group properties
in any molecule.
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