Fluid Phase Equilibria 338 (2013) 135–140

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Fluid Phase Equilibria

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Prediction of different thermodynamic properties for systems of alcohols and

sulfate-based anion Ionic Liquids using modified UNIFAC
Torben Hector, Lisa Uhlig, Jürgen Gmehling ∗
Carl von Ossietzky Universität Oldenburg, Technische Chemie, D-26111 Oldenburg, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Activity coefficients at infinite dilution in the temperature range between 303.15 K and 353.15 K,
Received 29 May 2012 vapor–liquid equilibria at 353.15 K and excess enthalpies at 353.15 K of binary systems containing
Received in revised form the Ionic Liquids 1-ethyl-3-methyl-imidazolium ethylsulfate [EMIM]+ [EtSO4 ]− , 1-ethyl-3-methyl-
15 September 2012
imidazolium methylsulfate [EMIM]+ [MeSO4 ]− and 1-ethyl-3-methyl-imidazolium hydrogensulfate
Accepted 1 November 2012
[EMIM]+ [HSO4 ]− have been measured. The obtained experimental data are used together with litera-
Available online 9 November 2012
ture data to fit modified UNIFAC interaction parameters between the sulfate anion and the main groups
OH and CH3 OH. The predictions are compared with the experimental values. Additionally an overview
Keywords:
Ionic Liquids
about the current status of the modified UNIFAC parameter matrix for Ionic Liquids is given.
Activity coefficients at infinite dilution © 2012 Elsevier B.V. All rights reserved.
Vapor–liquid equilibria
Excess enthalpies
Modified UNIFAC (Dortmund)

1. Introduction systematic measurements of activity coefficients at infinite dilution

Over the last couple of years there has been an increasing
interest in Ionic Liquids. Because of their specific properties, e.g.
negligible vapor pressure, high solubility of organic and inorganic
compounds, thermal stability, etc. Ionic Liquids are discussed as
alternative solvents in industrial processes, e.g. separation pro-
cesses. Because of the wide range of possible anions, cations, alkyl
rests and substituents the properties of the Ionic Liquids can be
adjusted for a specific problem. Therefore Ionic Liquids are also
called “Designer Solvents”. For the selection of the best suited Ionic
Liquid for a separation process the reliable knowledge of the phase
equilibrium behavior is required. Because of the wide range of pos-
sible cations, anions and substituents a reliable predictive model
would be desirable for the selection of the most suitable Ionic Liq-
uid.
This was the reason to extend the modified UNIFAC model to sys-
tems with Ionic Liquids. Modified UNIFAC (Dortmund) is a group
contribution model [1] for which a limited number of experimental
data are needed to fit the required group interaction parame-
ters. Even though there are some authors like Safarov et al. [2] or
Sumartschenkowa et al. [3], who published thermodynamic data,
the database for Ionic Liquids is still limited. To extend this database
∗ Corresponding author. Tel.: +49 441 798 3831; fax: +49 441 798 3330.
E-mail address: gmehling@tech.chem.uni-oldenburg.de (J. Gmehling).
URL: http://www.uni-oldenburg.de/tchemie (J. Gmehling).
( ∞ ), vapor–liquid equilibria (VLE) and excess enthalpies (HE ) are
carried out. This manuscript gives an overview about the exper-
imental methods, comparison between experimental results and
prediction using modified UNIFAC and a presentation of the current
status of the modified UNIFAC parameter matrix for Ionic Liquids.
2. Experimental
2.1. Materials and purities
The investigated Ionic Liquids [EMIM]+ [EtSO4 ]− ,
[EMIM]+ [MeSO4 ]− and [EMIM]+ [HSO4 ]− were obtained from
IOLITEC. To remove the last traces of volatile impurities, the Ionic
Liquids were treated by vacuum evaporation before use. Before
each dilutor experiment the purity was checked by taking a gas
phase sample before the solutes were added. Normally there
were no impurities or just very low (lower than the amounts of
infinite diluted components) amounts of known components. The
water contents of the Ionic Liquids were checked by Karl Fischer
Titration (<90 ppm). [EMIM]+ [EtSO4 ]− is able to react with water,
but in a test this behavior was only observed at higher amounts
of water and temperatures higher than 343.15 K. The investigated
alcohols methanol, ethanol, 1-propanol, 2-propanol, 1-butanol
and 2-butanol were obtained from VWR. All components and
their suppliers are listed in Table 1. For the dilutor experiments
the solutes are used without further purification since impurities
are separated in the column of the gas chromatograph and the

0378-3812/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2012.11.003
136 T. Hector et al. / Fluid Phase Equilibria 338 (2013) 135–140

Table 1 Table 3
Supplier and purity of the chemicals used. Experimental activity coefficients at infinite dilution of different alcohols in
[EMIM]+ [MeSO4 ]− .
Component Supplier Purity (% GC)
Solute T (K) i∞ Solute T (K) i∞
Methanol VWR 99.5
Ethanol VWR 99.9 Methanol 323.15 0.257 2-Propanol 323.15 1.334
1-Propanol VWR 99.9 333.15 0.203 333.15 1.172
2-Propanol VWR 99.8 343.15 0.178 343.15 1.006
1-Butanol VWR 99.9 353.15 0.105 353.15 0.840
2-Butanol VWR 99.8 Ethanol 323.15 0.449 1-Butanol 323.15 2.617
[EMIM]+ [EtSO4 ]− IOLITEC 333.15 0.398 333.15 2.403
[EMIM]+ [MeSO4 ]− IOLITEC 343.15 0.349 343.15 2.046
[EMIM]+ [HSO4 ]− IOLITEC 353.15 0.303 353.15 1.744
1-Propanol 323.15 1.053 2-Butanol 323.15 4.017
333.15 0.975 333.15 3.109
343.15 0.839 343.15 2.576
negligible amount in the measurement cell have no influence on 353.15 0.705 353.15 2.243
the quality of the results [4].
Uncertainty of the activity coefficients at infinite dilution approx. ±2.5%.
The purities of ethanol and 1-propanol were checked by gas
chromatography (99.9%). The water content was determined by
Karl Fischer titration (<90 ppm). Additionally for the VLE measure- 2.4. Excess enthalpies
ments all components were degassed at low pressure.
Using the Gibbs–Helmholtz equation partial molar excess
enthalpy data can be used to describe the temperature depend-
2.2. Activity coefficients at infinite dilution
ence of the acitvity coefficients. An isothermal flow calorimeter
from Hart Scientific (model 7501) was used for the measure-
For the measurement of  ∞ the dilutor technique was used.
ment of the excess enthalpies. In the literature [7] a detailled
A detailed description of the equipment and procedure is given
description of the apparatus and the measurement procedure
by Gruber et al. [5]. Because of their negligible vapor pressure
can be found. The experimental results for the excess enthalpies
the Ionic Liquids do not evaporate from the measurement cell, so
of the binary systems ethanol (1)–[EMIM]+ [EtSO4 ]− (2) and
that no additional saturation cell for the gas stream was required.
ethanol (1)–[EMIM]+ [MeSO4 ]− (2) are given in Table 6. The uncer-
The results of  ∞ for the solutes methanol, ethanol, 1-propanol,
tainty of the experimental excess enthalpies is approximately ±1%.
2-propanol, 1-butanol and 2-butanol measured in the Ionic Liq-
uids [EMIM]+ [EtSO4 ]− , [EMIM]+ [MeSO4 ]− and [EMIM]+ [HSO4 ]− are
given in Tables 2–4. The relative error using this method is approx- 3. Modified UNIFAC
imately ±2.5%.
Up to now for the cations imidazolium [RMIM]+ , pyri-
dinium [RPY]+ and pyrrolidinium [RMPYR]+ and the anions
2.3. Vapor–liquid equilibria bis(trifluoromethylsulfonyl)imide [BTI]− , trifluoromethanesul-
fonate [OTF]− , tetrafluoroborate [BF4 ]− , hexafluorophosphate
A computer-driven static apparatus, as described before [6], was [PF6 ]− and sulfate [RSO4 ]− parameters are available for modified
used to measure the binary vapor–liquid equilibria. The Px-data UNIFAC (Dortmund) (see Fig. 1). The group interaction parameters
for the binary systems ethanol (1)–[EMIM]+ [EtSO4 ]− (2) and 1- were fitted simultaneously to binary experimental data (VLE,  ∞ ,
propanol (1)–[EMIM]+ [EtSO4 ]− (2) at 353.15 K are listed in Table 5. HE , etc.) stored in the Dortmund Data Bank [8] and the systemati-
The repeatability and hysteresis of the pressure sensor are approx- cally measured data using the Simplex–Nelder–Mead method [9].
imately 0.005% of the maximum pressure. The temperature was The database was used for revision and extension of the existing
measured by a Hart Scientific 1506 thermometer using a Pt100 parameters [10,11]. Fig. 2 shows the present status of the modified
resistance sensor with a resolution of ±1 mK. UNIFAC parameter matrix for Ionic Liquids. The parameters used
for the following discussions are given in Table 7. In Table 8 the
Table 2 required van der Waals-values Rk and Qk are listed. The complete
Experimental activity coefficients at infinite dilution of different alcohols in revised parameter matrix for Ionic Liquids will be available soon
[EMIM]+ [EtSO4 ]− . [12].
Solute T (K) i∞ Solute T (K) i∞

Methanol 303.15 0.537 2-Propanol 303.15 1.477 Table 4

313.15 0.419 313.15 1.307 Experimental activity coefficients at infinite dilution of different alcohols in
323.15 0.406 323.15 1.247 [EMIM]+ [HSO4 ]− .
333.15 0.410 333.15 1.043
Solute T (K) i∞ Solute T (K) i∞
343.15 0.389 343.15 1.008
353.15 0.339 353.15 0.966 Methanol 323.15 0.087 2-Propanol 323.15 0.577
Ethanol 303.15 0.866 1-Butanol 313.15 1.934 333.15 0.078 333.15 0.356
313.15 0.783 323.15 1.651 343.15 0.058 343.15 0.278
323.15 0.703 333.15 1.386 353.15 0.041 353.15 0.223
333.15 0.600 343.15 1.367 Ethanol 313.15 0.426 1-Butanol 323.15 0.758
343.15 0.554 353.15 1.187 323.15 0.269 333.15 0.620
353.15 0.534 2-Butanol 303.15 2.065 333.15 0.177 343.15 0.430
1-Propanol 303.15 1.306 313.15 1.829 343.15 0.130 2-Butanol 323.15 1.219
313.15 1.204 323.15 1.686 353.15 0.116 333.15 0.760
323.15 1.029 333.15 1.565 1-Propanol 323.15 0.431 343.15 0.566
333.15 0.914 343.15 1.618 333.15 0.338 353.15 0.452
343.15 0.855 353.15 1.394 343.15 0.233
353.15 0.803 353.15 0.196

Uncertainty of the activity coefficients at infinite dilution approx. ±2.5%. Uncertainty of the activity coefficients at infinite dilution approx. ±2.5%
 T. Hector et al. / Fluid Phase Equilibria 338 (2013) 135–140 137

Table 5
Vapor–liquid equilibria for different alcohols and [EMIM]+ [EtSO4 ]− at 353.15 K.

x1 P (kPa) x1 P (kPa)

Ethanol (1)– 1-Propanol (1)–

[EMIM]+ [EtSO4 ]− [EMIM]+ [EtSO4 ]−
(2) (2)
0.0134 0.9917 0.0076 0.4045
0.0321 2.1193 0.0221 1.0022
0.0583 3.8300 0.0379 1.6580
0.0913 6.1170 0.0618 2.6710
0.1294 8.8830 0.0915 3.9620
0.1732 12.149 0.1300 5.6470
0.2288 16.507 0.1792 7.7840
0.2957 22.133 0.2387 10.418
0.3735 29.218 0.3107 13.603
0.4551 37.385 0.3891 17.133
0.5339 46.114 0.4679 20.789
0.6072 55.101 0.5438 24.585
0.6726 63.899 0.6137 28.403
0.7289 71.979 0.6757 32.119
0.7779 79.364 0.6912 33.360
0.8023 83.421 0.7311 35.716
0.8426 89.186 0.7426 36.228
0.8779 94.052 0.7888 38.933
0.9079 97.933 0.8303 41.435
0.9324 100.87 0.8667 43.615
0.9520 103.04 0.8974 45.372
0.9670 104.58 0.9230 46.723
0.9776 105.64 0.9432 47.703
0.9850 106.36 0.9585 48.376
0.9901 106.86 0.9699 48.853
0.9935 107.21 0.9779 49.153
0.9960 107.46 0.9841 49.380
0.9978 107.65 0.9893 49.573
0.9991 107.80 0.9918 49.648
1.000 107.88 1.000 50.075

Approximately ±0.005% repeatability of maximum pressure.

4. Results and discussion
The experimental activity coefficients of various alcohols
in [EMIM]+ [EtSO4 ]− and the predicted results using modified
UNIFAC are shown in Fig. 3. In addition to the experimental
data presented in this manuscript experimental data published
by Sumartschenkowa et al. [3] are shown. The experimen-
tal values are small. It can be seen that secondary alcohols
show slightly higher activity coefficients than primary alcohols.
This is not predicted by modified UNIFAC. The predicted tem-
perature dependence of the activity coefficients of methanol
and the other alcohols differ slightly since for methanol a
special group is used in the modified UNIFAC parameter
matrix.
In Figs. 4 and 5 the activity coefficients of the same alcohols
in [EMIM]+ [MeSO4 ]− and [EMIM]+ [HSO4 ]− are shown. Again the
small  ∞ -values are slightly different for the different isomeric C3 -
and C4 -alcohols. But the predicted temperature dependence and
dependence from the chain length is in good agreement with the
experimental data.
The binary vapor–liquid equilibria of ethanol and 1-propanol
with [EMIM]+ [EtSO4 ]− at 353.15 K and the predicted results using
modified UNIFAC are shown in Fig. 6. It can be seen that ethanol
with the Ionic Liquid show negative deviation from Raoult’s law,

Table 6
Excess enthalpies for ethanol with different Ionic Liquids at 353.15 K.

x1 HE (J mol−1 ) x1 HE (J mol−1 )
−
+
Ethanol (1)-[EMIM] [EtSO4 ] (2) Ethanol (1)-[EMIM] [MeSO4 ]− (2)
+

0.0627 108.568 0.0977 138.119

0.1063 186.545 0.1834 254.558
0.1471 266.280 0.2490 349.215
0.1979 353.452 0.3794 559.328
0.2670 457.468 0.5247 772.677
0.3288 574.238 0.6059 860.741
0.4017 700.394 0.7010 910.446
0.4504 757.638 0.7779 876.160
0.5480 862.757 0.8414 767.138
0.6281 915.325 0.8947 587.177
0.7203 916.008 0.9358 380.591
0.7937 856.199 0.9754 159.355
0.8535 729.843
0.9032 545.224
0.9412 344.365
0.9776 136.931

Uncertainty of excess enthalpy measurements less than 1%.

138 T. Hector et al. / Fluid Phase Equilibria 338 (2013) 135–140

1.5

0.5

ln
-0.5

-1.5
2.75 2.95 3.15 3.35
1000/T [K-1]

Fig. 3. Experimental and predicted activity coefficients of methanol (), ethanol

(䊉), 1-propanol (), 2-propanol (×), 1-butanol () and 2-butanol (+) (experimental
data this work) and methanol (), ethanol (), 1-propanol (), 2-propanol ( ), 1-
butanol (♦) and 2-butanol (–) (experimental data [3]) in [EMIM]+ [EtSO4 ]− . Modified
UNIFAC (—).

2.5

1.5

0.5
ln

Fig. 1. Cations and anions incremented for modified UNIFAC.

-0.5

while for the system with 1-propanol nearly ideal behavior is

observed. The predicted results are in qualitative agreement with -1.5
the experimental data at low alcohol concentrations and show
slightly higher deviations from the experimental values at higher
alcohol concentrations. -2.5
Figs. 7–9 show the experimental binary vapor–liquid equilibria 2.75 2.85 2.95 3.05 3.15
of methanol (Fig. 7), ethanol (Fig. 8) and 1-propanol (Fig. 9) with 1- 1000/T [K-1 ]
butyl-3-methyl-imdiazolium octylsulfate [BMIM]+ [OcSO4 ]− in the
temperature range between 298.15 K and 313.15 K published by Fig. 4. Experimental and predicted activity coefficients of methanol (), ethanol
Safarov et al. [2] and the predicted results using modified UNIFAC. (䊉), 1-propanol (), 2-propanol (), 1-butanol () and 2-butanol (♦) in
[EMIM]+ [MeSO4 ]− . Modified UNIFAC (—).

0.5

-0.5

-1.5
ln

-2.5

-3.5
2.75 2.85 2.95 3.05 3.15
1000/T [K -1]

Fig. 5. Experimental and predicted activity coefficients of methanol (), ethanol (䊉),
1-propanol (), 2-propanol (), 1-butanol () and 2-butanol (♦) in [EMIM]+ [HSO4 ]− .
Modified UNIFAC (—).
Fig. 2. Current status of modified UNIFAC parameter matrix for Ionic Liquids [12].
 T. Hector et al. / Fluid Phase Equilibria 338 (2013) 135–140 139

120 8

7
100
6
80
5
P [kPa]

P [kPa]
60 4

3
40
2
20
1
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
x1 x1
Fig. 6. Experimental and predicted vapor–liquid equilibria for ethanol () and 1-
Fig. 9. Experimental and predicted vapor–liquid equilibria for 1-propanol (1) with
propanol (䊉) (1) with [EMIM]+ [EtSO4 ]− (2) at 353.15 K. Modified UNIFAC (—).
[BMIM]+ [OcSO4 ]− (2) at 298.15 K (), 303.15 K (䊉), 308.15 K () and 313.15 K ().
Experimental data [2]. Modified UNIFAC (—).
40

35 It can be seen, that the predicted results are in agreement with the
experimental data.
30 The excess enthalpies of ethanol and [EMIM]+ [EtSO4 ]− respec-
tively [EMIM]+ [MeSO4 ]− at 353.15 K and their prediction with
25 modified UNIFAC are shown in Fig. 10. Both systems are described
very well by the modified UNIFAC model.
P [kPa]

20

15 Table 7
Used group interaction parameters for modified UNIFAC (Dortmund).

10 Main groups Group interaction parameters

1 2 a12 (K)a21 (K) b12 b21 c12 (K−1 )c21 (K−1 )

5
CH2 Imidazolium 70.3800 0.24511 –
77.7793 0.83298
0 CH2 Sulfate 1859.3741 4.06308 –
0 0.2 0.4 0.6 0.8 1 1131.3051 −0.93175
OH Imidazolium 292.6468 −1.59145 –
x1 147.0663 2.08343
OH Sulfate 225.0235 −4.32710 0.0030855
Fig. 7. Experimental and predicted vapor–liquid equilibria for methanol (1) with 448.3810 −1.61662 0.0005180
[BMIM]+ [OcSO4 ]− (2) at 298.15 K (), 303.15 K (䊉), 308.15 K () and 313.15 K (). CH3 OH Imidazolium −704.2285 −1.26236 0.0149627
Experimental data [2]. Modified UNIFAC (—). 152.7192 2.17856 −0.0098745
CH3 OH Sulfate 1037.5603 −5.46099 –
20 1421.5572 0.34143
Imidazolium Sulfate −113.0145 −1.48378 –
18 −35.9320 −1.52136
16
14
Table 8
12 Modified UNIFAC (Dortmund) relative van der Waals volumes Rk and surface areas
P [kPa]

10 Qk for the groups used.

8 Main group Subgroup Rk Qk

6 CH2 [13] CH3 0.6325 1.0608

CH2 0.6325 0.7081
4 CH 0.6325 0.3554
2 C 0.6325 0.0000
OH [13] OH (p) 1.2302 0.8927
0 OH (s) 1.0630 0.8663
0 0.2 0.4 0.6 0.8 1 OH (t) 0.6895 0.8345
x1 CH3 OH [13] CH3 OH 0.8585 0.9938
Imidazolium C3 H3 N2 1.8430 1.6997
Fig. 8. Experimental and predicted vapor–liquid equilibria for ethanol (1) with C3 H2 N2 1.3662 0.6797
[BMIM]+ [OcSO4 ]− (2) at 298.15 K (), 303.15 K (䊉), 308.15 K () and 313.15 K (). Sulfate SO4 0.9903 3.5249
Experimental data [2]. Modified UNIFAC (—). HSO4 1.5654 3.8076
140 T. Hector et al. / Fluid Phase Equilibria 338 (2013) 135–140

1200 Furthermore this paper gives an idea about present status of the
modified UNIFAC parameter matrix for Ionic Liquids. The revised
parameter matrix contains group interaction parameters for 72
1000
group pairs with Ionic Liquids. Gaps in the parameter matrix with
the pyrrolidinum and pyridinium cations as well as for the triflu-
800 ormethanesulfonate and the tetrafluoroborate anions have been
closed. In addition the sulfate and the hexafluorophosphate anions
hE [J/mol]

600 were added as new main groups and interaction parameters have
been fitted for them, too. For fitting the parameters the systemat-
ically measured data together with activity coefficients at infinite
400 dilution, vapor–liquid equilibria and excess enthalpies stored in the
Dortmund Data Bank were used.
200 It was shown that systems with Ionic Liquids can be predicted
reliably with the modified UNIFAC model. This means that the
model can be applied for the design of various industrial processes
0 using Ionic Liquids.
0 0.2 0.4 0.6 0.8 1
x1 Acknowledgments

Fig. 10. Experimental and predicted ecxess enthalpies for ethanol (1) with
The authors would like to thank R.Bölts for experimental assis-
[EMIM]+ [EtSO4 ]− () and [EMIM]+ [MeSO4 ]− (䊉) (2) at 353.15 K. Modified UNIFAC
(—). tance. We also thank IOLITEC for supplying the Ionic Liquids.

5. Conclusion
Activity coefficients at infinite dilution for methanol,
ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol in
the Ionic Liquids [EMIM]+ [EtSO4 ]− , [EMIM]+ [MeSO4 ]− and
[EMIM]+ [EtSO4 ]− , vapor–liquid equilibria of ethanol and 1-
propanol with [EMIM]+ [EtSO4 ]− and excess enthalpies of ethanol
with [EMIM]+ [EtSO4 ]− and [EMIM]+ [MeSO4 ]− have been measured
to extend the data base required to fit the group interaction param-
eters of the modified UNIFAC method. The new experimental data
together with the data stored in the Dortmund Data Bank were
used to fit the group interaction parameters between the sulfate
main group and the main groups OH and CH3 OH.
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