ARTICLE

pubs.acs.org/IECR

Activity Coefficients of Organic Solutes at Infinite Dilution in Ionic

Liquids. 1. 1-Hexyl-3-Methylimidazolium Hexafluorophosphate and
1-Octyl-3-Methylimidazolium Hexafluorophosphate and Their Application
to Alkane/Aromatic and Aromatic/Aromatic Hydrocarbon Separation
Yi Li, Li-Sheng Wang,* Yun-Xia Feng, and Chun-Yuan Zhang
School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, People’s Republic of China

bS Supporting Information
ABSTRACT: Activity coefficients at infinite dilution, γ∞ i,3, for organic solutes (alkanes, alkenes, alkyl benzenes, alcohols, chloro-
methanes, acetonitrile, ethyl acetate, dioxane, tetrahydrofuran, and acetone) in 1-hexyl-3-methylimidazolium hexafluorophosphate
[HMIM][PF6] and 1-octyl-3-methylimidazolium hexafluorophosphate [OMIM][PF6] have been determined using gas
liquid
chromatography at temperatures from 303.15 to 363.15 K with the ionic liquids as the stationary phase. The partial molar excess
enthalpies at infinite dilution of the ionic liquids were calculated for the solutes from the temperature dependence of the
experimental activity coefficients at infinite dilution. The solubility parameters of ionic liquids were also determined by the regular
solution theory. The selectivities of various ionic liquids for the alkane/aromatic hydrocarbon and aromatic/aromatic were
summarized from literature and calculated from γ∞ i,3.

’ INTRODUCTION studied so far, and the solutes are only 17 and 24 when the IL is
Ionic liquids (ILs) have been studied intensively in recent [HMIM][PF6] and [OMIM][PF6], respectively.
years. The capability of ILs to separate organic mixtures is of great This work is a continution of a study on the determination
importance for the development of separation processes. Activity of activity coefficients γ∞ i,3 at infinite dilution of various solutes

coefficient is a fundamental thermodynamic quantity which can
provide a convenient measure of solution nonideality, as well
as provide information on the intermolecular energy between
solvent and solute. Selectivity of the ILs with the organic solu-
tes can be calculated from the activity coefficients at infinite
dilution of solutes in ILs. The properties of ILs can be changed
by varying the structure of the cations and anions such as
alkyl rests and functional groups. As a designable green solvent,
physicochemical and thermophysical properties of ILs have
been studied systematically by various research groups in the
past years.
The activity coefficients at infinite dilution of solutes in ionic
liquids with an alkyl carbon chain in the cations have been studied
when the anion is [BF4].1
8 The change of the infinite dilution
activity coefficients of hydrocarbons and alcohols, with the
number of carbon atoms contained in the cation aliphatic chain,
has been discussed. The results indicate that the γ∞i,3 values decrease
as the length of the IL alkyl chain increases.4 It is necessary to
estimate the effect of changing alkyl chain when the anion is not
[BF4]. The prediction using thermodynamic theory such as linear
solvation energy relationship (LSER)9 and universal functional
activity coefficient method (UNIFAC) is helpful when the correla-
tion parameters are given. The correlation of parameters requires
sufficient experiment data of different solutes to reach the smaller
relative deviations. The γ∞i,3 values of solutes in 1-alkyl-3-methyli-
midazolium hexafluorophosphate ([CnMIM][PF6]) ILs: [BMIM]-
[PF6],10
12 [HMIM][PF6],13 and [OMIM][PF6],14 have been
(i) by the gas
liquid chromatographic method (GC) for ionic
liquids 1-hexyl-3-methylimidazolium hexafluorophosphate
([HMIM][PF6]) and 1-octyl-3-methylimidazolium hexafluor-
ophosphate ([OMIM][PF6]). In this work, the γ∞ i,3 values of
solutes with more and different functional groups have been
determined using GC method.
The selectivities of various ionic liquids for the alkane/
aromatic and aromatic/aromatic will be summarized from
literature and calculated from the γ∞ i,3 data, including the data
measured in this work. Currently in the petrochemical in-
dustry sulfolane has been widely used as aromatic extraction
solvent. However, the sulfolane should be replaced because of
its volatility and flammability. The selectivity of sulfolane for
the alkane/aromatic hydrocarbons needs to be improved. The
goal of this work is to search the possibility of using ionic
liquid to replace sulfolane as aromatic extraction solvent. The
structure
property relationship of ILs and the variations of
the selectivity with the change of molecular structure of the
ILs, such as cation and anion species, the chain length, and
polarity of chain of the functional group, need to be system-
atically studied. The results will be helpful not only for the
theoretical improvement but also for the process design of the
chemical engineering community.
Received: December 9, 2010
Accepted: August 19, 2011
Revised: June 29, 2011
Published: August 19, 2011

r 2011 American Chemical Society 10755 dx.doi.org/10.1021/ie102458k | Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research ARTICLE

Table 1. Experimental Activity Coefficients at Infinite Dilution of Organic Solutes in the Ionic Liquid [HMIM][PF6] as the
Stationary Phase from 303.15 to 363.15 K
solute T/ K = 303.15 T/K = 313.15 T/K = 323.15 T/K = 333.15 T/K = 343.15 T/K = 353.15 T/K = 363.15

nonane 93.092 77.042 62.683 53.293 48.407 42.662 37.883

methylcyclohexane 43.515 31.133 22.001 18.691 14.929 13.062 10.597
cyclohexene 11.858 10.014 8.532 7.334 6.361 5.566 4.915
styrene 2.146 2.100 2.057 2.017 1.976 1.948 1.916
ethylbenzene 4.400 4.199 3.957 3.813 3.669 3.518 3.380
o-xylene 4.093 3.876 3.686 3.533 3.385 3.236 3.113
m-xylene 5.089 4.796 4.424 4.185 3.928 3.746 3.604
p-xylene 4.682 4.409 4.171 3.953 3.752 3.618 3.426
1-propanol 2.479 2.411 2.340 2.282 2.228 2.183 2.133
1-pentanol 4.380 4.080 3.824 3.592 3.411 3.213 3.056
2-methylpropanol 3.423 3.285 3.164 3.051 2.934 2.858 2.772
2-butanol 4.148 4.041 3.942 3.852 3.771 3.695 3.623
acetonitrile 1.944 1.959 1.974 1.986 1.998 2.010 2.019
ethyl acetate 3.927 4.233 4.486 4.685 5.063 5.457 5.911
tetrahydrofuran 2.674 2.810 2.931 3.094 3.176 3.486 3.618
1,4-dioxane 2.254 2.334 2.412 2.504 2.605 2.717 2.840
dichloromethane 0.784 0.800 0.822 0.844 0.860 0.878 0.894
trichloromethane 0.528 0.565 0.620 0.672 0.710 0.775 0.837
tetrachloromethane 4.582 4.908 5.304 5.723 6.289 6.902 7.637

’ EXPERIMENTAL SECTION of (0.0001 g. To avoid possible residual adsorption effects of

Materials. The ionic liquids [HMIM][PF6] and [OMIM]-
[PF6] were purchased from Shanghai Cheng Jie Chemical Co.,
Ltd. with a purity of 99.5%, according to manufacturer’s speci-
fications with impurities, mass fractions of chlorine: w (Cl
) <
5  10
4; water mass fractions analyzed by Karl Fischer analysis
were less than 6  10
4. To confirm the purity of the ILs, the
chemical shifts for the 1H NMR spectrum (parts per million,
C3D6O) were determined and they appear as follows: [HMIM]-
[PF6], δ: 9.07 (s, 1H, CH
N), 7.73
7.66 (d, 2H, CHdCH
N),
4.16
4.12 (t, 2H, CH2Me), 3.84 (s, 3H, CH3N), 1.79
1.74
(t, 2H, CH2N), 1.26
1.22 (m, 6H, (CH2)3), 0.87
0.84 (t, 3H,
CH2CH3); [OMIM][PF6], δ: 9.07 (s, 1H, CH-N), 7.74
7.67
(d, 2H, CHdCH-N), 4.15
4.12 (t, 2H, CH2Me), 3.84 (s, 3H,
CH3N), 1.80
1.76 (t, 2H, CH2N), 1.26
1.23 (m, 10H,
(CH2)5), 0.86
0.84 (t, 3H, CH2CH3). The solutes provided
by Beijing Chemical Reagents Company were all analytical
reagents and were used without further purification. Dry
helium was used as the carrier gas, and tetrahydrofuran was
used as solvent to coat the ionic liquid onto the solid support,
as the ILs could not dissolve well in alcohols. Chromosorb W/
AW-DMCS 100/120 mesh was used as solid support for the
ionic liquid in the GC column. The purity of the ionic liquids
was higher than 99%.
Experimental Procedure. The GC method was used for
the measurements of infinite dilution activity coefficients in
ionic liquid. Helium was used as carrier gas. The retention
time for the solute was obtained from the differences be-
tween the standard time and the detected time for solute.
Coating the solid support material with the ionic liquid was
performed by dispersing a certain portion of chromosorb in a
solution of the ionic liquid in tetrahydrofuran followed by
evaporation of the solvent using a rotating evaporator. The
mass of the stationary phase was determined with a precision
10756
the solutes on chromosorb, the amount of ionic liquid was
60% mass fraction related to the support material. The
column was filled uniformly with the help of an ultrasound
vibrator.
Before experiment the column was conditioned by blow-
ing carrier gas through at high flow rate at a high temperature
(about 423 K) for about 24 h. The solute was injected as a
liquid to the injector at temperature 443 K. The value of the
dead time t G was determined with methane as the nonretain-
able pure component under the assumption that the effect of
the solubility of methane in the ionic liquid was negligible.
Each experiment was repeated at least twice at a given
temperature to check the reproducibility. Retention times
were generally reproducible within 0.01
1 min.
The GC was equipped with a thermal conductivity detec-
tor (TCD). The flow rate was stabilized for at least 30 min
before any measurement was made. The inlet column pres-
sure was determined by inner manometer. Outlet pressure
was kept equal to atmospheric pressure. To check the stabi-
lity of the experimental condition, such as no occurrence of
elution of the stationary phase by the helium stream, mea-
surement of retention time was repeated every 60 h for
hexane and benzene. No changes in the retention time were
observed for the duration of 1 month. No measurements
were taken for 1-pentanol at 303.15 K and 3-methylbutanol
at (303.15, 313.15) K because of their long retention times.
The measurements for other solutes were all carried out at
temperatures from 303.15 to 363.15 K.
Experimental Uncertainties. Retention time, dead time,
column temperature, flow rate, input and output pressure,
and the mass of the stationary phase all have experimental
errors. The error limits of the flow rate U0 were estimated to
be (0.5% at column temperature and (0.01% at the flow
meter temperature. The error limits of the input pressure
dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research ARTICLE

Table 2. Experimental Activity Coefficients at Infinite Dilution of Organic Solutes in the Ionic Liquid [OMIM][PF6] as the
Stationary Phase from 303.15 to 363.15 K
solute T/K = 303.15 T/K = 313.15 T/K = 323.15 T/K = 333.15 T/K = 343.15 T/K = 353.15 T/K = 363.15

methylcyclohexane 9.086 8.781 8.457 8.294 8.125 7.861 7.658

2,2,4-trimethylpentane 19.045 17.731 16.218 15.262 14.224 13.483 12.750
cyclohexene 4.784 4.672 4.568 4.477 4.378 4.302 4.227
styrene 1.817 1.837 1.863 1.885 1.912 1.929 1.950
o-xylene 2.882 2.839 2.801 2.771 2.736 2.708 2.672
m-xylene 3.428 3.352 3.289 3.228 3.171 3.118 3.070
p-xylene 3.651 3.581 3.517 3.456 3.394 3.353 3.302
1-propanol 1.582 1.470 1.378 1.274 1.154 1.086 1.014
1-butanol 1.560 1.474 1.410 1.332 1.256 1.192 1.136
1-pentanol 1.382 1.350 1.316 1.292 1.266
2-propanol 1.886 1.768 1.670 1.582 1.496 1.410 1.368
2-methylpropanol 1.497 1.447 1.398 1.354 1.312 1.278 1.244
2-butanol 1.681 1.630 1.586 1.546 1.504 1.472 1.440
3-methylbutanol 1.602 1.524 1.456 1.384 1.324 1.282
acetonitrile 0.761 0.773 0.787 0.801 0.818 0.835 0.854
ethyl acetate 1.883 1.908 1.935 1.982 2.026 2.077 2.131
acetone 1.117 1.137 1.153 1.171 1.187 1.202 1.217
tetrahydrofuran 1.840 1.907 1.989 2.102 2.218 2.325 2.438
1,4-dioxane 3.268 3.505 3.784 4.098 4.481 4.836 5.109
dichloromethane 0.663 0.685 0.707 0.729 0.751 0.771 0.791
trichloromethane 0.468 0.508 0.557 0.609 0.658 0.708 0.761
tetrachloromethane 2.340 2.456 2.604 2.725 2.861 2.978 3.094

Table 3. Coefficients of Equation 4, a and b, van der Waals Volumes of Solvent (ri), Solubility Parameters of Solute (δi), Activity
Coefficients at Infinite Dilution (γ∞
i at 298.15 K) of Solutes in [HMIM][PF6] Using eq 4, Values of Hi
E,∞
Derived from eq 5, and
Standard Deviation σ
solute i ria/cm3 3 mol
1 δia/(J 3 cm
3)0.5 a b/K γ∞
i at 298.15 K HE,∞
i /kJ 3 mol
1 σ

nonane 98.95 15.527
0.891 1635.92 99.055 13.602 0.0626

methylcyclohexane 70.46 16.27
4.606 2518.29 46.549 20.938 0.1280
cyclohexene 88.69 14.051
2.867 1619.04 12.977 13.462 0.0019
styrene 66.25 19.127 0.073 209.22 2.171 1.740 0.0035
ethylbenzene 69.74 18.043
0.103 480.19 4.516 3.993 0.0131
o-xylene 70.66 18.453
0.238 499.23 4.205 4.151 0.0092
m-xylene 70.66 18.09
0.636 690.71 5.371 5.743 0.0275
p-xylene 70.66 17.838
0.323 565.51 4.828 4.702 0.0184
1-propanol 42.17 24.557 0.016 266.03 2.509 2.212 0.0033
1-pentanol 62.63 22.576
0.774 686.38 4.608 5.707 0.0231
2-methylpropanol 52.39 23.751
0.051 390.77 3.496 3.249 0.0066
2-butanol 52.39 22.63 0.604 247.06 4.205 2.054 0.0006
acetonitrile 28.37 24.094 0.896
70.12 1.937
0.583 0.0010
ethyl acetate 52.77 18.346 3.755
726.96 3.731
6.044 0.0187
tetrahydrofuran 44.62 19.129 2.804
555.59 2.561
4.619 0.0262
1,4-dioxane 44.62 20.163 2.190
420.8 2.178
3.499 0.0015
dichloromethane 34.71 20.378 0.567
245.43 0.772
2.041 0.0048
trichloromethane 43.5 19.028 2.137
845.02 0.498
7.026 0.0240
tetrachloromethane 52.3 17.577 4.573
933.54 4.229
7.762 0.0077
a
Values obtained from literature.22

Pi and the output pressure Po were estimated to be (0.6% virial coefficient estimation was 2
5%. Based on the error
and (0.02%, respectively. The uncertainty of determining propagation law, γ∞ i,3 was estimated to have a relative uncer-
n3 was estimated to be (0.5%. The uncertainty of the cross tainty within (5%.
10757 dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research ARTICLE

Table 4. Coefficients of Equation 4, a and b, van der Waals Volumes of Solvent (ri), Solubility Parameters of Solute (δi), Activity Coefficients
at Infinite Dilution (γ∞
i at 298.15 K) of Solutes in [OMIM][PF6] Using eq 4, Values of Hi
E,∞
Derived from eq 5, and Standard Deviation σ
solute i ria/cm3 3 mol
1 δia/(J 3 cm
3)0.5 a b/K γ∞
i at 298.15 K HE,∞
i /kJ 3 mol
1 σ

methylcyclohexane 70.46 16.27 1.199 305.00 9.222 2.536 0.0104

2,2,4-trimethylpentane 88.69 14.051 0.497 742.44 19.830 6.173 0.0125
cyclohexene 57.04 17.611 0.814 227.82 4.846 1.894 0.0017
styrene 66.25 19.127 1.030
131.58 1.801
1.094 0.0026
o-xylene 70.66 18.453 0.609 136.28 2.904 1.133 0.0023
m-xylene 70.66 18.09 0.566 201.81 3.465 1.678 0.0008
p-xylene 70.66 17.838 0.686 184.59 3.688 1.535 0.0021
1-propanol 42.17 24.557
2.270 830.04 1.681 6.901 0.0282
1-butanol 52.4 23.289
1.481 586.17 1.624 4.874 0.0164
1-pentanol 62.63 22.576
0.541 279.50 1.493 2.324 0.0087
2-propanol 62.62 21.671
1.347 600.50 1.949 4.993 0.0476
2-methylpropanol 52.39 23.751
0.724 340.25 1.527 2.829 0.0039
2-butanol 52.39 22.63
0.419 285.33 1.707 2.372 0.0040
3-methylbutanol 62.62 22.322
1.177 516.43 1.741 4.294 0.0091
acetonitrile 28.37 24.094 0.417
211.02 0.748
1.754 0.0008
ethyl acetate 52.77 18.346 1.378
229.19 1.839
1.906 0.0071
acetone 39.04 19.774 0.626
156.06 1.108
1.298 0.0009
tetrahydrofuran 44.62 19.129 2.339
528.94 1.759
4.398 0.0233
1,4-dioxane 44.62 20.163 3.962
846.45 3.074
7.038 0.0318
dichloromethane 34.71 20.378 0.660
324.99 0.651
2.702 0.0018
trichloromethane 43.5 19.028 2.204
900.12 0.443
7.484 0.0086
tetrachloromethane 52.3 17.577 2.561
519.01 2.270
4.315 0.0063
a
Values are obtained from literature.22

Figure 1. Plot of ln γ∞i of [HMIM][PF6] versus 1/T for the following

solutes: 9, nonane; b, methylcyclohexane; 2, cyclohexene; 1, styrene; (,
ethylbenzene; 0, o-xylene; O, m-xylene; Δ, p-xylene; — linear correlation.
’ THEORETICAL BASIS
Figure 2. Plot of ln γ∞
i of [HMIM][PF6] versus 1/T for the following
solutes: 9, 1-propanol; b, 1-pentanol; 2, 2-methylpropanol; 1, 2-bu-
tanol; 0, acetonitrile; O, ethyl acetate; Δ, tetrahydrofuran; 3, 1,4-
dioxane; (, dichloromethane; ), trichloromethane;  , tetrachloro-
methane; — linear correlation.

The equation proposed by Everett15 in 1965 and Cruickshank

et al.16 in 1966 was used for obtaining the γ∞
i,3 for a volatile solute where R (J 3 K
1 3 mol
1) is the gas constant, T (K) is the
(i) in an involatile solvent (3) from GC results: temperature, γ∞ i,3 is the activity coefficient of solute i at infinite
dilution in the stationary phase 3, P0i (kPa) is the vapor pre-


n3 RT B11
Vi0 0 2B12
Vi∞ ssure of the pure liquid solute i, and n3 is the number of moles
ln γ∞
i, 3 ¼ ln 0
Pi þ JPout of the stationary phase component on the column. The second
VN Pi RT RT
and third terms in eq 1 are correction terms that arise from the
ð1Þ nonideality of the mobile gaseous phase. B11 (cm3 3 mol
1) is
10758 dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research
Figure 3. Plot of ln γ∞
i [OMIM][PF6] versus 1/T for the followin solutes:
9, methylcyclohexane; b, 2,2,4-trimethylpentane; 2, cyclohexene; 1,
styrene; (, o-xylene; 0, m-xylene; O, p-xylene; Δ, dichloromethane; 3,
trichloromethane;  , tetrachloromethane. — linear correlation.
Figure 4. Plot of ln γ∞ i [OMIM][PF6] versus 1/T for the following
solutes: 9, 1-propanol; b, 1-butanol; 2, 1-pentanol; 1, 2-propanol; (,
2-methylpropanol; 0, 2-butanol; O, 3-methylbutanol; Δ acetonitrile; 3,
ethyl acetate; ), acetone;  , tetrahydrofuran; +, 1,4-dioxane; — linear
correlation.
3
the second virial coefficient of the solute, B12 (cm 3 mol ) is
1
the cross second virial coefficient of the solute (1) with the
carrier gas (2), V0i (cm3 3 mol
1) is the liquid molar volume of
pure solute, and V∞ 3
1
i (cm 3 mol ) is the partial molar volume
of the solute in the ionic liquid at infinite dilution. VN
(cm3 3 mol
1) is the standardized retention volume defined by
" #
Tcol Pw0
VN ¼ JU0 ðtr
tG Þ 1
ð2Þ
Tf Pout
where tr (min) is the retention time, tG (min) is the dead
time, U0 (mL 3 min
1) is the flow rate, measured by a soap
bubble flow meter, Tcol (K) is the column temperature, Tf (K)
is the flow meter temperature, P0w (kPa) is the vapor pressure
10759
ARTICLE
Figure 5. Plot of ln γ∞
i of solutes in [CnMIM][PF6] as a function of
carbon chain n: 9, cyclohexene; O, m-xylene; Δ, 1-propanol; 2,
dichloromethane; 3, trichloromethane; 1, tetrachloromethane. The
ln γ∞
i of solutes in [BMIM][PF6] are obtained from refs 10
12.
Figure 6. Residual function Y for [HMIM][PF6] and [OMIM][PF6]
versus solute solubility parameters δi. Regression line: Y = 18.145 δi

221057 for [HMIM][PF6] and Y = 17.631 δi
208693 for [OMIM][PF6].
9, for Y versus δi of [OMIM][PF6]; b, for Y versus δi of [HMIM][PF6].
of water at Tf (K), and Pout (kPa) is the pressure at the column
outlet. The pressure correction term J appearing in eq 1 and
eq 2 is given by20

" #
3 ðPin =Pout Þ2
1
J ¼ ð3Þ
2 ðPin =Pout Þ3
1
where Pin and Pout are the inlet and outlet pressures of the GC
column, respectively.
The data for calculating the correction terms have been
obtained in the following way. For all solutes, values of P0i
were calculated from the Antoine equation, with Antoine
constants given by Boublik et al.17 Molar volumes of solutes
V0i were estimated using experimental values of their densities;
partial molar volumes of solute at infinite dilution V∞ i were
assumed to be equal to V0i . The third term of eq 1 is much less
dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research ARTICLE

than the first and second terms, the γ∞ i,3 calculated from the The partial molar excess enthalpy at infinite dilution (HE,∞
i ) was
partial molar volume is similar to the assumed V∞ i . Values of B11 calculated from Gibbs
Helmholtz equation
and B12 were estimated based on the equations suitable for
nonpolar liquids by Tsonopolous’ method18 with an uncertainty ∂ln γ∞ H E, ∞
i, 3
¼ i ð5Þ
of < (10 cm3 3 mol
1. The critical parameters needed for the ∂ð1=TÞ R
calculations were available from the literature.18 The mixed
where the partial derivatives of ln γ∞ i with respect to 1/T were
critical properties Pcij, Tcij, Vcij, and Zcij and mixed acentric factor
obtained from the slope of a straight line derived from eq 4.
ωij were calculated by using equations given in the literature.18,19
The selectivities, S∞
ij can be calculated from the equation given
The outlet pressure Pout was kept equal to the atmospheric
by
pressure.
The results of γ∞ i,3 were correlated with temperature by the S∞ ∞ ∞
ij ¼ γi3 =γj3 ð6Þ
following equation
The activity coefficients at infinite dilution can be represented
b by a two-term eq 7: the combinatorial term (ln γ∞comb
i ) can be
ln γ∞
i, 3 ¼ a þ ð4Þ represented by the modification21 to Flory’s equation, the
ðT=KÞ
residual term (ln γ∞res
i ) is given by the regular solution theory:
Table 5. Solubility Parameters of the Ionic Liquids ln γ∞ ∞comb
i ¼ ln γi þ ln γ∞res
i ð7Þ
δs  104/(J 3 m
3)1/2 a ln γ∞comb
i ¼ ln½ðri =rs Þ2=3  þ 1
ðri =rs Þ2=3 ð8Þ
IL this work ref 4 ref 24 ref 25 ref 26 ref 27
ln γ∞res
i ¼ ðvi =RTÞðδi
δs Þ2 ð9Þ
[EMIM][Tf2N] 1.93 2.75 2.27 3
1
[BMIM][Tf2N] 2.09 2.65 2.13
where ri (cm 3 mol ) is the van der Waals volumes of solute; rs
(cm3 3 mol
1) is the van der Waals volumes of solvent; vi
(cm3 3 mol
1) is the solute molar volume; δi (J 3 cm
3)0.5 and
[HMIM][Tf2N] 1.95 2.52 2.06
[BMIM][BF4] 2.43 2.48 2.65
δs (J 3 cm
3)0.5 are the solubility parameters of solute and solvent,
[HMIM][BF4] 2.33 respectively. Information on vi, δi, and ri was obtained from the
[OMIM][BF4] 2.25 2.66 2.66 2.66 literature.22 The van der Waals volumes of ILs were calculated by
[BMIM][PF6] 2.27 2.95 2.51 2.53 group contribution method.23
[HMIM][PF6] 2.44 A residual function Y can be rearranged from eq 9:4
[OMIM][PF6] 2.37
ln γ∞res δi 2 2δs δs 2
a
Values are at 25 °C, except those estimated in refs 25 and27, which are Yi ¼
i
þ ¼ δi
ð10Þ
at 30 °C. vi RT RT RT

Table 6. Selected Ionic Liquids Used in the Calculations for Alkane/Aromatic and Aromatic (1)/Aromatic (2) Hydrocarbon
Separation Problems
ionic liquid abbreviation ref

1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM] [BF4] 33

1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] 34
1-hexadecyl-3-methylimidazolium tetrafluoroborate [C16MIM] [BF4] 35
1-ethyl-3-methylimidazolium trifluoromethanesulfonate [EMIM] [TfO] 36
1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM] [TfO] 37
1-hexyl-3-methylimidazolium trifluoromethanesulfonate [HMIM] [TfO] 38
1-methyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [MMIM] [NTf2] 39
1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM] [NTf2] 39
1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM] [NTf2] 39
n-ethylpyridinium bis(trifluoromethylsulfonyl)imide [EPY] [NTf2] 40
1-methyl-3-methylimidazolium methylsulfate [MMIM] [MeSO4] 40
1-ethyl-3-methylimidazolium methylsulfate [EMIM] [MeSO4] 39
1-ethyl-3-methylimidazolium ethylsulfate [EMIM] [ESO4] 39
1-methyl-3-methylimidazolium methoxyethylsulfate [MMIM] [MASO4] 40
1-methyl-3-methylimidazolium dimethylphosphate [MMIM] [(CH3)2PO4] 40
1-propyl-2,3-dimethylimidazolium tetrafluoroborate [PDMIM][BF4] 28
1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate [HydEMIM][BF4] 29
1-butyl-3-methylimidazolium trifluoromethanesulfonate [BMIM][CF3SO3] 30
1-(methyl)acryloyloxyalkyl-3-methylimidazolium bromide [MAOOMIM]Br 31
1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM][PF6] this work
1-octyl-3-methylimidazolium hexafluorophosphate [OMIM][PF6] this work

10760 dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764

Industrial & Engineering Chemistry Research ARTICLE

Table 7. Selectivities S∞
12 of Alkanes (1)/Aromatic (2) Hydrocarbon for Ionic Liquids and Sulfolane at T = 323.15 K

ionic liquid S∞
12

(2)

(1) benzene toluene ethylbenzene o-xylene m-xylene p-xylene

[PDMIM][BF4]a n-pentane 38.58 22.52 10.80 15.34 11.80 12.49

n-hexane 59.88 34.95 16.76 23.81 18.32 19.39
n-heptane 98.56 57.52 27.58 39.19 30.15 31.91
n-octane 152.13 88.79 42.57 60.48 46.53 49.26
n-nonane 192.86 112.56 53.97 76.68 58.99 62.45
n-decane 1212.94 707.91 339.43 482.24 371.01 392.74
cyclohexane 26.67 15.57 7.46 10.60 8.16 8.64
methylcyclo- hexane 43.00 25.10 12.03 17.10 13.15 13.92
2,2,4-trimethylpentane 106.76 62.31 29.87 42.44 32.65 34.57
[HydEMIM][BF4]b n-heptane 131.51 67.48 30.67 43.14 33.69 35.24
n-octane 63.10 32.38 14.72 20.70 16.17 16.91
n-nonane 63.99 32.84 14.93 20.99 16.39 17.15
cyclohexane 53.65 27.53 12.52 17.60 13.75 14.38
methylcyclo- hexane 46.32 23.77 10.80 15.20 11.87 12.41
2,2,4-trimethyl-pentane 80.34 41.23 18.74 26.36 20.58 21.53
[BMIM][CF3SO3]c, cyclopentane 12.89 8.65 5.54 6.59 5.59 5.77
cyclohexane 19.94 13.38 8.57 10.19 8.64 8.93
cycloheptane 27.42 18.40 11.78 14.02 11.88 12.28
cyclononane 38.87 26.08 16.70 19.87 16.84 17.41
[HMIM][PF6]d nonane na na 15.84 17.01 14.17 15.03
methylcyclo- hexane na na 5.56 5.97 4.97 5.28
[OMIM][PF6]d methylcyclo- hexane na na na 3.02 2.57 2.41
2,2,4-trimethylpentane na na na 5.79 4.93 4.61
sulfolanee n-pentane 14.97 9.79 6.50 na na na
n-hexane 20.52 13.41 8.90 na na na
n-heptane 26.94 17.61 11.69 na na na
cyclohexane 12.52 8.18 5.43 na na na
methylcyclo- hexane 17.36 11.35 7.53 na na na
a
Ref 28. b Ref 29. c Ref 30 (328.15 K). d This work. e Ref 32; na: not analyzed.

The values of experimental γ∞ were obtained from this work,
the values of ln γ∞comb were calculated by eq 8, the solubility
parameters δi of different solutes are already known, then the
values of Yi for each solvent were calculated by eq 10. Equation 10
shows that there is a linear relation between Yi and the solute
solubility parameter δi for a given solvent and temperature T.
The value of the solvent solubility parameter δs can be obtained
from the slope of this line.
’ RESULTS AND DISCUSSION
The values of γ∞ i,3 of solutes in [HMIM][PF6] and [OMIM]-
[PF6] obtained over a temperature range from 303.15 to 363.15 K
are listed in Tables 1 and 2. The coefficients a and b, γ∞ i,3 at the
standard condition (T = 298.15 K) calculated using eq 4, the
standard deviation σ of the fitted equation, and values of HE,∞
derived from eq 4 are listed in Tables 3 and 4. The plots of
measured ln γ∞ i,3 vs 1/T values are given in Figures 1, 2, 3, and 4.
The γ∞ i,3 values for 1-pentanol and 3-methylbutanol were not
measured at the temperature 303.15 K and 303.15, 313.15 K,
respectively, because the retention times were far beyond
the scope allowed by GC. Figure 5 shows the activity coeffi-
cients at infinite dilution of cyclohexene, m-xylene, 1-propanol,
dichloromethane, trichloromethane, and tetrachloromethane
in [CnMIM]PF6 (n = 4, 6, 8) ionic liquids at 313.15 K. The γ∞ i,3
decreased with the increasing of carbon chain length on the
cations. HE,∞
i was positive and increased with the chain length
of the linear alkanes.
The linear dependence between Yi and δi obtained from the
γ∞ data on [HMIM][PF6] and [OMIM][PF6] is displayed in
Figure 6. The solubility parameters of these two ILs calculated
by this procedure, and the reported solubility parameters4,24
27
of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide
[CnMIM][Tf2N] and 1-alkyl-3-methylimidazolium tetrafluorobo-
rate [CnMIM][BF4], are listed in Table 5. Besides the solubility
parameters reported by ref 24, the other data show that the value
of solubility parameter will decrease with the carbon chain length
on the cation with same anion.
i The selectivities of various ionic liquids and sulfolane for
the alkane/aromatic hydrocarbon, and various ionic liquids
for aromatic/aromatic are summarized from literature and
calculated from the γ∞ i,3 data. The candidate ILs included
1-alkyl-3-methyllimidazolium tetrafluoroborate ([CnMIM]-
[BF4]),33
35 1-alkyl-3-methyllimidazolium trifluoromethanesul-
fonate ([CnMIM][TfO]),36
38 1-alkyl-3-methyllimidazolium
bis(trifluoromethylsulfonyl)imide ([C nMIM][NTf2]), 39 and
10761 dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research ARTICLE

Table 8. Selectivities S∞
12 of Aromatic (1)/Aromatic (2) Hydrocarbon for Ionic Liquids at T = 323.15 K

ionic liquid S∞
12

(2)

(1) benzene toluene ethylbenzene o-xylene m-xylene p-xylene

[MAOOMIM]Bra benzene 0.457 0.193 0.279 0.210 na

toluene 2.190 0.422 0.613 0.461 na
ethylbenzene 5.190 2.370 1.447 1.089 na
o-xylene 3.581 1.632 0.691 0.756 na
m-xylene 4.762 2.170 0.918 1.323 na
[HydEMIM][BF4]b benzene 0.513 0.233 0.328 0.256 0.268
toluene 1.950 0.455 0.639 0.499 0.522
ethylbenzene 4.290 2.20 1.406 1.099 1.149
o-xylene 3.048 1.564 0.711 0.781 0.817
m-xylene 3.903 2.003 0.910 1.281 1.046
p-xylene 3.732 1.915 0.870 1.224 0.956
[HMIM][PF6]c ethylbenzene na na 1.074 0.894 0.949
o-xylene na na 0.932 0.833 0.884
m-xylene na na 1.118 1.200 1.061
p-xylene na na 1.054 1.132 0.943
[OMIM][PF6]c o-xylene na na na 0.852 0.796
m-xylene na na na 1.174 0.935
p-xylene na na na 1.256 1.069
a
Ref 31. b Ref 29. c This work; na: not analyzed.

1-alkyl-3-methyllimidazolium methylsulfate.40 Four ionic liquids:
[PDMIM][BF4],28 [HydEMIM][BF4],29 [BMIM][CF3SO3],30
and [MAOOMIM]Br31 are found to have significant separa-
tion effect for the alkane/aromatic hydrocarbon and aromatic/
aromatic separation problems. They are listed in Table 6
together with the ionic liquids [HMIM][PF6 ] and [OMIM]-
[PF6] investigated in this work.
The selectivities of [CnMIM][BF4],33
35 [CnMIM][TfO],
38
and [CnMIM][NTf2]39 for the alkane/aromatic hydrocarbon
mixtures separation show that the selectivity increases with
increasing of number of organic groups on the cation. The values
of selectivities decrease with increasing number of carbon atoms
of aliphatic chain on cation for this separate problem. The
comparison of [HMIM][PF6] and [OMIM][PF6] in Table 7
confirms this phenomenon. Table 7 shows that most of the
investigated ionic liquids can be used as aromatic extraction
solvents from alkane/aromatic hydrocarbon mixtures. The se-
lectivities S∞
ij of [PDMIM][BF4] (with three organic groups on
the cation) are higher than other ILs (with two organic groups
on the cation). All ionic liquids listed in Table 7 show good
separation ability, [PDMIM][BF4] and [HydEMIM][BF4] are
much better than the experimental selectivities of sulfolane.32
Table 8 shows the selectivities S∞ 12 of ionic liquids for
aromatic/aromatic hydrocarbon mixtures. The results of selec-
tivity by using [HMIM][PF6] and [OMIM][PF6] to separate m-
xylene (1) and o-xylene (2), the results of S∞12 are slightly different
from 1.200 to 1.174, and for p-xylene (1) and o-xylene (2) the
results of S∞12 are different from 1.132 to 1.256. Compared with
the [BMIM][BF4],34 by increasing the polarity of chain on
cation, for example using [HydEMIM][BF4] to separate the
mixture of xylenes, higher selectivities are obtained. The result of
selectivity for the mixture of m-xylene (1) and o-xylene (2) is
S∞ ∞
12 = 1.281 and for p-xylene (1) and o-xylene (2) is S12 = 1.224.
10762
From Table 8, it can be seen that [MAOOMIM]Br has the
highest selectivity only for separation of m-xylene (1) and o-
xylene (2), for which the result is S∞
12 = 1.323.
For the comparison of type of anions, the IL with [BF4] will be
better than that with [PF6] for the same kind of cations. This is
probably because the hydrophobic properties of [PF6] are higher
than [BF4].
Currently the experimental data are not enough; more activity
coefficient data at infinite dilution for different ionic liquids are
required to improve the understanding on the structures of ILs
and their selectivity.
’ CONCLUSIONS
Activity coefficients at infinite dilution of selected organic
solutes in two ionic liquids [HMIM][PF6] and [OMIM][PF6]
have been measured at the temperature range from 303.15 to
363.15 K. From the results of measurements for the two ILs, the
γ∞i,3 value decreases with increasing of carbon chain length on the
cations. The partial molar excess enthalpies at infinite dilution
of the ionic liquids were calculated for the solutes from the
temperature dependence of the experimental activity coefficients
at infinite dilution. The value of HE,∞i was positive and increased
with the chain length of the linear alkanes. The solubility para-
meters of ionic liquids were also determined by the regular
solution theory. Solubility parameters decrease with the carbon
chain length on the cation of ionic liquid with same anion. The
selectivities of various ionic liquids for the alkane/aromatic and
aromatic/aromatic were summarized from literature and calcu-
lated from γ∞ i,3 obtained in this study. The results show applic-
ability of the ILs to separation processes, and the selectivity
shows potential of ILs for application to petrochemical separa-
tion processes. Currently the experimental data are not enough,
dx.doi.org/10.1021/ie102458k |Ind. Eng. Chem. Res. 2011, 50, 10755–10764
Industrial & Engineering Chemistry Research ARTICLE

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