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The investigation of the infinite dilution activity coefficients for molecular

Publikacja / Publication compounds in 1-(3-hydroxypropyl)-3-methyl-imidazolium thiocyanate,
Królikowski Marek, Królikowska Marta, Markowski Cezary
DOI wersji wydawcy / Published version DOI http://dx.doi.org/10.1016/j.jct.2021.106554
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Identyfikator publikacji / Publication identifier WUT908c5a172e944f47b739d4f7d97f0149
Królikowski Marek, Królikowska Marta, Markowski Cezary: The
investigation of the infinite dilution activity coefficients for molecular
Cytuj tę wersję / Cite this version compounds in 1-(3-hydroxypropyl)-3-methyl-imidazolium thiocyanate,
Journal of Chemical Thermodynamics, Academic Press, vol. 161, 2021,
Article number: 106554, pp. 1-10, DOI:10.1016/j.jct.2021.106554
 J. Chem. Thermodynamics 161 (2021) 106554

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

The investigation of the infinite dilution activity coefficients for

molecular compounds in 1-(3-hydroxypropyl)-3-methyl-imidazolium
thiocyanate
Marek Królikowski a,b,⇑, Marta Królikowska a,b, Cezary Markowski a
a
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
b
Thermodynamic Research Unit, School of Engineering, University of KwaZulu-Natal, Howard College, Campus, Durban, South Africa

a r t i c l e i n f o a b s t r a c t
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Article history: Measurements of infinite dilution activity coefficients of 46 organic solutes including alkanes, alkenes,
Received 28 February 2021 alkynes, aromatic hydrocarbons, alcohols, ethers, ketones, pyridine, thiophene, acetonitrile, and 1-
Received in revised form 8 June 2021 nitropropane in ionic liquids (IL), 1-(3-hydroxypropyl)-3-methyl-imidazolium thiocyanate (abbreviated
Accepted 12 June 2021
as [C1C3OHIM][SCN]) are reported in the temperature range from T = (318.15 to 358.15) K. Based on
Available online 16 June 2021
the experimental data, the infinite dilution capacity and selectivity of the studied IL are presented to eval-
uate the effectiveness of using it as an extractant in the separation of aliphatic from aromatic hydrocar-
Keywords:
bons and sulfur compounds from alkanes. Obtained selectivity and capacity values for different
Infinite dilution activity coefficient
[C1C3OHIM][SCN]
separation processes are compared with the literature data for other ionic liquids. From the temperature
Selectivity, capacity – dependence of the infinite dilution activity coefficient, the partial molar excess Gibbs energy, DGE;1 1 ,
Extraction process enthalpyDHE;1
1 and entropy term T ref DSE;1
1 at infinite dilution were calculated and discussed.
Thermodynamics properties at infinite Ó 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://
dilution creativecommons.org/licenses/by/4.0/).

1. Introduction and fungicidal compounds, drug carriers, additives for food, wood
impregnation agents, in separation techniques on a large industrial
Ionic liquids are organic salts that have aroused exceptional scale, as well as in environmental cleaning technologies [3,4,5].
interest in application research over the last two decades. Typically Literature reports show that ionic liquids show high values of
they are defined as compounds that show a melting point below selectivity coefficients for the separation of aliphatic hydrocarbons
373 K [1]. Ionic liquids consist of a large organic, often unsymmet- from aromatic or aromatic sulfur compounds (thiophene) from ali-
rical cation and a smaller organic or inorganic anion [2]. Extremely phatic hydrocarbons (fuels) in comparison with classic organic sol-
low volatility and several unique properties of ionic liquids, i.e. low vents used on an industrial scale (N-methyl-2-pyrrolidone, or
vapor pressure, non-flammability, high thermal and chemical sta- sulfolane) [6], which is combined with negligible vapor pressure,
bility, high heat capacity, the wide temperature range for the liquid makes possible to use ionic liquids as extractants in extraction pro-
state, and complete or partial miscibility in water and other cesses. To be able to plan technological processes with the use of
organic solvents make them extremely attractive from the point ionic liquids, including the extraction processes mentioned above,
of view of research vision and application in future technologies. it is necessary to create a wide experimental database on thermo-
An additional advantage of the chemistry of ionic liquids is the dynamic and physicochemical properties of pure ionic liquids, as
ability to control and improve the physical and chemical properties well as their binary and ternary systems with commonly used
of these types of compounds by appropriate selection of the cation organic solvents (n-alkanes, aromatics, thiophene, or pyridine).
and anion structure of ionic liquids. Such action enables the design The basic research in this field includes the experimental work
of new, targeted media. Particularly low volatility speaks for the and modeling of phase equilibria in binary [7,8] and ternary
use of ionic liquids as alternative solvents in many branches of [10–12] systems as well as density and viscosity measurements
the chemical industry, including chemical synthesis, extraction, [13,14], important from the point of view of future technological
and separation, as electrolytes in batteries, lubricants, bactericidal applications.
Fundamental information about suitable solvents for different
⇑ Corresponding author at: Department of Physical Chemistry, Faculty of Chem-
separation processes can be obtained from the infinite dilution
istry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland.
activity coefficients (c1 13 ) measurements, performed using the

E-mail address: mkrolikowski@ch.pw.edu.pl (M. Królikowski). gas–liquid chromatography technique. The knowledge of the c1 13

https://doi.org/10.1016/j.jct.2021.106554
0021-9614/Ó 2021 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

is the first step in the search for ionic liquids, the best for the sep- et al. [38]. The synthesis was carried out using drying socket
aration of various types of mixtures, hence also in estimating the instead of nitrogen. In the procedure, acetone was used instead
extraction capacity of the ionic liquid. Based on the measurements of dichloromethane due to low solubility of synthesized com-
of the activity coefficients in the infinite dilution, the selectivity pounds in dichloromethane.
1
ðS112 Þ and capacity (k2 Þ are determined, which are used to deter-
mine the potential ability of ionic liquids as solvents in extraction
processes. The IL-based separations most intensively evaluated
2.1.1.1. Synthesis of 1-(3-hydroxypropyl)-3-methylimidazolium chlo-
based on c1 13 are aromatic from aliphatic hydrocarbons [15–17] sul- ride, [C1C3OHIM][Cl].. To a round flask with a volume of 250 cm3
phur compounds (thiophene) from aliphatic hydrocarbons (model
equipped with a condenser and a drying socket,
fuel) [18–20], alkenes from alkanes [21,22], or 1-butanol from
a mass of 70.65 g of 1-methyl-3-H-imidazole (0.8605 mol, Io-Li-
water [23,24].
Tec 98%, used as recieved), 90.02 g 3-chloropropanol (0.9522 mol,
This work presents new experimental data of the infinite dilution
Sigma-Aldrich 98%, 11% excess, used as received), and 100 cm3 of
activity coefficients of 46 organic solutes including n-alkanes,
acetonitrile (Avantor, 99,99%) were added. The mixture was stirred
cycloalkanes, alken-1-es, alkyn-1-es, aromatic hydrocarbons, alco-
for 48 h in the oil bath at T = 363.2 K. Product was crystallized from
hols, ethers, ketones, and other polar compounds. These compounds
ethanol added drop wise into an ethyl acetate acetone mixture (1:3
were dissolved in the novel IL namely: 1-(hydroxypropyl)-3-methy
ratio). Obtained solid was washed with diethyl ether. Product was
limidazolium thiocyanate, [C1C3OHIM][SCN]. The experiment was
obtained as a mass of 81.84 g of crystalline solid. The reaction yield
performed at a wide temperature range using the GLC technique.
was 53.8% (0.4633 mol).
Based on the in silico approach [6] the ILs functionalized by 1
H NMR dH(500 MHz; D2O) ppm: 2.022 (2H, m), 3.521 (2H, t, 3JH,
cyano-, or hydroxy group were suggested as a potentially effective 3
H = 5.87 Hz), 3.806 (3H, s), 4.206 (2H, t, JH,H = 7.1 Hz), 7.352–7.416
extractant in the separation of aliphatic from aromatic hydrocar-
(2H, m), 8.657 (1H, s).
bons or in the desulfurization of model fuel. Furthermore, this paper 13
C NMR dC(100 MHz; D2O) ppm: 31.667, 35.783, 46.505, 57.942,
is a continuation of our systematic studies on the impact of IL’s struc-
122.339, 123.662, 136.087.
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ture on the activity coefficients at infinite dilution of molecular com-

pounds dissolved in them. This work extends the study on
thiocyanate-based ILs, as a promising extractant in many separation
processes, especially in the desulfurization of gasoline [25,26]. In the 2.1.1.2. Synthesis of 1-(3-hydroxypropyl)-3-methylimidazolium thio-
previous studies using SCN-based ILs, only a non-functionalized salt cyanate, [C1C3OHIM][SCN]. To a round flask with a volume of
with the following cations: 500 cm3, a mass of 40.10 g 1-(3-hydroxypropanyl)-3-methylimida
1-ethyl-3-methylimidazolium ([EMIM]+) [27], 1-butyl-3- zolium chloride (0.2370 mol, synthesized), 19.22 g sodium thio-
methylimidazolium ([BMIM]+) [28], 1-hexyl-3-methylimidazolium cyanate (0.2371 mol, Sigma-Aldrich 98%, used as received) and
([HMIM]+) [29], 1-butyl-1-methylpyrrolidinium ([BMPYR]+) [30], 200 cm3 of demineralized water were added. The mixture was stir-
1-butyl-4-methylpyridinium ([BMPy]+) [30], and 1-butyl-1- red for 2 h at room temperature. Afterwards water was removed by
methylpiperidinium ([BMPIP]+) [31] were investigated, thus data rotary evaporation and the obtained solid was further dried in vac-
presented here will be a valuable supplement to knowledge in the uum at T = 373 K for 24 h. To the flask 150 cm3 of dry acetone and
field of properties of this class of ionic liquids. This paper discusses 3 g of charcoal were added. The mixture was stirred for 2 h. After-
the extraction efficiency of the [C1C3OHIM][SCN] against the back- wards the mixture was filtered on a column filled with 4 g of silica
ground of not only other SCN-type ionic liquids mentioned above gel. Solvent was removed by rotary evaporation and further dried
but also of the salt with the dicyanamide anion including 1-butyl- in vacuum at T = 373 K for 24 h. Product was obtained as a mass
3-methylimidazolium dicyanamide, [BMIM][DCA] [32], 1-hydroxy of 40.14 g of oil. The reaction yield was 85.0% (0.2015 mol).
1
propyl-3-methylimidazolium dicyanamide, [C1C3OHIM][DCA] [33], H NMR dH(500 MHz; D2O) ppm: 2.108 (2H, m), 3.614 (2H, t, 3JH,
1-hydroxyethyl-3-methylimidazolium dicyanamide, [C1C2OHIM] H = 6.1 Hz), 3.909 (3H, s), 4.306 (2H, t, 3JH,H = 7.1 Hz), 7.451–7.510
[DCA] [34], 1-chloroethyl-3-methylimidazolium dicyanamide, [C1- (2H, m), 8.737 (1H, s).
13
C2ClIM][DCA] [34], 1-butyl-4-methylpyridinium dicyanamide, C NMR dC(100 MHz; D2O) ppm: 31.940, 36.009, 46.730, 58.159,
[BMPy][DCA] [35], (3-cyanopropyl)pyridinium dicyanamide, [C3CN- 122.487, 123.825, 133.006, 136.235.
Py][DCA] [36], 1-butyl-1-methylpyrrolidinium dicyanamide, The NMR spectra are presented in Figures from S1 to S4 in Sup-
[BMPYR][DCA] [37] and 1-(cyano-propyl)-1-methylpyrrolidinium plementary Materials (SM).
dicyanamide, [C1C3CNPYR][DCA] [36]. The chloride content of [C1C3OHIM][SCN] was analyzed using X-
ray fluorescence spectrometry (XRF) on the Rigaku NEX QC + appa-
ratus. The method was described by us earlier [9]. The measure-
2. Experimental section ment uncertainty was lower than 20 ppm. The experiment was
performed three times, and the average result is presented in
2.1. Materials. Table 2.
Before the experiment, the sample of IL was dried under vac-
The chemical structure and basic thermophysical characteriza- uum at a temperature of 353 K for 48 h with vigorous stirring. This
tion of the IL tested in this work are presented in Table 1. Ionic liq- procedure was applied to remove moisture and the volatile com-
uid has been synthesized in this work. The final product was pounds present in the samples. No decomposition of the IL was
analyzed by 1H NMR and 13C NMR spectra. A detailed description observed at the experimental conditions. The water mass fraction
of the synthesis procedure and NMR analysis is given below. of the dried IL was determined using Karl-Fischer titration (model
SCHOTT Instruments TitroLine KF used with CombiTitrant 2 sup-
2.1.1. Synthesis procedure plied by Merck). The sample description, including the purities,
The synthesis of 1-(3-hydroxypropyl)-3-methylimidazolium water content, and purification methods, is presented in Table 2.
thiocyanate, [C1C3OHIM][SCN] was carried out by metathesis reac- The solutes were used without further purification because the
tion with sodium thiocyanate of 1-(3-hydroxy-propyl)-3-methyli GLC technique separated any solutes impurities on the column. A
midazolium chloride, [C1C3OHIM][Cl]. Chloride salt was synthesized complete list of them, including sources and mass fraction purities,
according to modified literature procedure presented by Dupont is given in Table S1 in the SM.
2
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

Table 1
Structure, Name, Abbreviation, Molar mass (M), Glass Transition Temperature (Tg) and Heat Capacity Change at Glass Transition Temperature (DC pðgÞ ) at Pressure, p = 0.1 MPa of
the Investigated Ionic Liquid.a

Structure Name, Abbreviation M/ Tg / K DC pðgÞ /

g∙mol1 J∙mol1∙K1
1-(3-hydroxypropyl)-3-methylimidazolium thiocyanate 199.27 187.6 140
[C1C3OHIM][SCN]

a
Standard uncertainties u are as follows: u(Tg) = 0.3 K; u(DC pðgÞ ) = 5 J∙mol1∙K1; u(p) = 10 kPa.

Table 2
Specifications of Chemical Sample.

Sample Source water content/ Chloride Initial mass fraction Purification method Final mass fraction Analysis method
ppm content/ppm purity purity
[C1C3OHIM][Cl] Own    Crystallization, vacuum  0.950 Karl-Fischer, 1H
synthesis heating NMR
[C1C3OHIM][SCN] Own 410 1640  Vacuum heating  0.950 Karl-Fischer, 1H
synthesis NMR, XRF
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2.2. Apparatus and procedure methanol had completely evaporated from the IL-coated solid
before making up the column. Immediately before the experiment,
2.2.1. Differential scanning calorimetry (DSC) measurements each column was conditioned. The stream of helium was passed
Differential scanning calorimetry (DSC) technique was used to through the column at a high flow rate, about 2 cm3s1, and at
determine the thermophysical properties of pure IL such as glass temperature T = 358.15 K for 8 h. The flow rate of the carrier gas
transition temperature (Tg) and heat capacity at glass transition was determined using a soap bubble flow meter which was placed
(DCp(g)). The experiment was performed in heating mode using at the outlet after the detector. The flow rate was set for a series of
DSC 1 STARe System (Mettler Toledo) calorimeter. The detailed runs and was allowed to stabilize for at least 15 min before any c1 13
description of the apparatus and calibration method was described determinations were made. The flow rates were corrected for
earlier [9]. The accuracy of the calibration is u(T) = 0.3 K, u(DCp water vapor pressure and ranged from (0.25 to 1.40) cm3s1.
1 1
(g)) = 5 Jmol K . The sample was sealed in ambient air in a her- The pressure drop was varied between 20 and 50 kPa depending
metic aluminum pan, having a mass of about 50 mg. An empty her- on the flow rate of the carrier gas. The estimated overall error in
metic aluminum pan was used as a reference. A sample size of c1
13 was less than 5%, taking into account the possible errors in
about 10 mg was used throughout this study and the heat flow determining the column loading, the retention times, and solute
was normalized by the actual weight of each sample. The experi- vapor pressure.
ments were carried out over a temperature range from T = (140 The infinite dilution activity coefficients for solute (1) partition-
to 320) K with a 10 Kmin1 heating rate. The experimental data ing between a carrier gas (2) and ionic liquid (3) were determined
were analysed using STAR software and are collected in Table 1. based on the data on retention of molecular solutes through GC
The DSC plots are presented in Fig. S5 in SM. glass column filled with IL-coated solid support. The retention data
were treated in terms of Everett-Cruickshank equations [40,41]
given below:
2.2.2. Infinite dilution activity coefficient measurements
 

3
The activity coefficients at infinite dilution for molecular com- n3 RT B11  V 1 p1 2B12  V 1
1 J 2 po
pounds in [C1C3OHIM][SCN] were experimentally determined at a lnc1
13 ¼ ln  þ ð1Þ
V N p1 RT RT
wide temperature range from T = (318.15 to 358.15) K ± 0.02 K
with an increment of 10 K by gas–liquid chromatography. The where n3 is the number of mole of IL on the column packing, R is the
experiment was performed using PerkinElmer Clarus 480 chro- Universal Gas Constant, T is the column temperature, VN denotes
matograph equipped with a TCD detector. The data were collected the net retention volume of the solute, p1 is the saturated vapor
and processed using the TotalChrom Workstation software. To per- pressure of the solute at temperature T, B11 is the second virial coef-
form the experiment, a glass column of length 1 m and 4 mm inter- ficient of pure solute, V 1 is the molar volume of the solute, B12 is the
nal diameter was used. The detailed description of method and mixed second virial coefficient of the solute and the carrier gas, V 1 1
equipment was described earlier [39]. Chromosorb W/AW-DCMS is the partial molar volume of the solute at infinite dilution in the
100/120 mesh (supplied by Sigma-Aldrich) was the solid support. solvent and J 32 p0 is the mean column pressure. The virial coefficients
The masses of the stationary phase and solid support were values B11 and B12 and critical parameters for most of the solutes
weighed using a Mettler Toledo AB 204-S balance, with a precision needed for the calculation of c1 13 were taken from the literature [42].
of ± 1∙104 g. In the present work, the solvent column packing was The activity coefficient at infinite dilution is defined as [39]
45.40% (1.082 mmol) and 49.01% (1.296 mmol) mass percent of the
IL. This large column loading prevents possible residual adsorption def
c1
13 ¼ limx1 !0 c1 ðP ! 0Þ ð2Þ
of solute onto the column packing. The average values of the two
columns were presented as the result. For each temperature, the Pressure equal to zero is also a part of the standard state (i.e.,
measurements were repeated by using two different columns with pure liquid solute at zero pressure). That is a hypothetical state
different mass percent packing. Care was taken to ensure that the of the solute.
3
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

From the temperature dependence of c1 13 , the partial molar The partial molar excess Gibbs free energy at infinite dilution,
excess thermodynamic functions at infinite dilution are calculated DG1E;1 was calculated using the following equation:
from the following equations:
DGE;1
1 ¼ DHE;1
1  T DSE;1
1 ð5Þ
1

DH1E;1 DSE;1
ln c13 ¼  1
ð3Þ From experimental activity coefficients at infinite dilution, two
RT R
of the most important parameters in designing an effective extrac-
1
In the investigated temperature range, the temperature depen- tion process such as selectivity, S1
12 and capacity, k2 were deter-
dence of c113 can be shown by the linear van’t Hoff relation given mined for different separation problems using the following
by: equations:

a c1
ln c1
13 ¼ þb ð4Þ S1
12 ¼
13
ð6Þ
T c1
23

where the partial molar excess enthalpy at infinite dilution,

1 1
DH1E;1 and partial molar excess entropy at infinite dilution, DS1E;1 k2 ¼ ð7Þ
can be obtained from the slope and the intercept, respectively.
c1
23

Table 3
Temperature Dependence of the Average Experimental Infinite Dilution Activity Coefficient (c1
13 ) for Molecular Solutes in [C1C3OHIM][SCN].
a,b

Solutes T/K b u(b) a/K u(a) / K R2

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318.15 328.15 338.15 348.15 358.15

c1
13

n-Heptane 790 690 618 1322 55 2.51 0.17 0.998

n-Octane 1040 940 840 760 684 1196 25 3.193 0.074 0.999
n-Nonane 1370 1240 1130 1040 950 1035 11 3.970 0.034 0.999
n-Decane 1730 1590 1482 1370 1272 871 15 4.719 0.044 0.999
Cyclohexane 175 150 132 117 104 1464 17 0.555 0.052 1.000
Methylcyclohexane 288 254 226 201 181 1328 10 1.491 0.030 1.000
Cycloheptane 201 177 155 138 124 1385 13 0.950 0.040 1.000
Cyclooctane 268 235 212 189 168 1312 27 1.466 0.079 0.999
Cyclohexene 49.0 45.8 42.7 40.2 38.0 728.5 7.3 1.602 0.022 0.999
Hept-1-ene 289 264 242 223 207 956.7 1.7 2.659 0.050 1.000
Oct-1-ene 463 424 392 365 340 875.2 7.6 3.385 0.023 0.999
Dec-1-ene 957 894 835 780 733 761 10 4.474 0.030 0.999
Pent-1-yne 14.5 14.4 14.3 14.2 14.1 79.60 1.8 2.424 0.005 0.999
Hex-1-yne 24.5 24.2 23.9 23.6 23.3 145.5 3.0 2.742 0.009 0.999
Hept-1-yne 44.1 43.2 42.5 41.7 40.9 211.8 5.7 3.121 0.017 0.998
Oct-1-yne 76.6 74.5 73.0 71.3 69.9 257.4 4.2 3.528 0.012 0.999
Benzene 5.50 5.47 5.45 5.42 5.40 54.41 0.63 1.535 0.002 0.999
Toluene 9.81 9.82 9.83 9.84 9.85 9.858 0.058 2.3145 0.0002 1.000
Ethylbenzene 19.6 19.3 19.0 18.8 18.6 149.5 3.3 2.505 0.010 0.999
o-Xylene 15.1 14.9 14.7 14.5 14.3 163.2 2.3 2.201 0.007 0.999
m-Xylene 19.0 18.9 18.8 18.7 18.6 58.30 1.5 2.761 0.005 0.999
p-Xylene 18.0 17.8 17.7 17.5 17.4 103.3 2.0 2.565 0.006 0.999
Styrene 7.31 7.36 7.41 7.45 7.50 70.9 1.0 2.212 0.003 1.000
Alpha-methylstyrene 13.2 13.4 13.6 13.9 14.1 196.5 4.0 3.194 0.012 0.999
Methanol 0.718 0.701 0.685 0.670 0.655 260.8 3.4 1.150 0.010 1.000
Ethanol 1.49 1.44 1.39 1.34 1.30 389.2 1.7 0.825 0.005 1.000
Propan-1-ol 2.33 2.22 2.13 2.05 1.97 473.6 5.6 0.644 0.016 0.999
Propan-2-ol 2.46 2.38 2.31 2.23 2.16 370.3 6.9 0.262 0.020 0.999
Butan-1-ol 3.80 3.58 3.40 3.20 3.05 629 11 0.641 0.033 0.999
Thiophene 2.82 2.86 2.89 2.93 2.97 145.5 5.4 1.493 0.016 0.999
Tetrahydrofuran 3.97 3.98 3.99 4.00 4.01 28.54 0.55 1.486 0.002 0.999
1,4-Dioxane 2.08 2.14 2.21 2.27 2.33 326.0 4.8 1.756 0.014 0.999
tert-Butyl methyl ether 33.2 32.2 31.4 30.4 29.5 333 10 2.457 0.030 0.997
tert-Butyl ethyl ether 115 109 102 96.8 91.0 669 20 2.649 0.058 0.996
tert-Pentyl methyl ether 55.0 53.4 52.0 50.5 49.2 317.5 5.0 3.010 0.015 0.999
Di-n-ethyl ether 28.7 27.5 26.6 25.6 24.5 444 12 1.963 0.037 0.998
Di-n-propyl ether 124 117 110 104 99.0 644.6 7.9 2.792 0.023 1.000
Di-n-butyl ether 333 313 290 272 253 788 23 3.339 0.068 0.998
Acetone 2.27 2.29 2.31 2.33 2.35 98.6 1.7 1.129 0.005 0.999
Pentan-2-one 7.00 6.96 6.91 6.87 6.83 70.10 0.51 1.726 0.002 1.000
Pentan-3-one 7.05 7.08 7.11 7.14 7.16 44.10 0.49 2.092 0.001 1.000
Hexan-2-one 11.3 11.4 11.4 11.4 11.4 20.03 0.39 2.490 0.001 0.999
Hexan-3-one 12.5 12.6 12.7 12.9 13.0 102.9 3.5 2.848 0.010 0.997
Acetonitrile 1.37 1.38 1.38 1.39 1.39 41.26 0.78 0.444 0.002 0.999
Pyridine 1.04 1.08 1.12 1.17 1.21 431 11 1.391 0.032 0.998
1-Nitropropane 3.57 3.58 3.60 3.61 3.63 47.50 0.89 1.420 0.003 0.999
a
For hypothetical liquid solute at zero pressure.
b
The standard uncertainties u are as follows: for infinite dilution activity coefficient u(c1
13 ) = 5%, for temperature u(T) = 0.02 K. b, a / K are coefficient of Eq. (4), u(b), u(a) / K
are standard uncertainty of coefficient of Eq. (4). R2 is the coefficient of determination.

4
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

3. Results and discussion values of the infinite dilution activity coefficient. Delocalized p
electrons in aromatic hydrocarbons allow interacting with IL which
The average values of the infinite dilution activity coefficient, results in a significantly lower value of c1 13 in comparison to alipha-
obtained for 46 molecular compounds in [C1C3OHIM][SCN] are pre- tic hydrocarbons. Moreover, cyclization of the alkane skeleton
sented in Table 3. reduces the value of c1 13 in comparison to that of the corresponding
The measurements were carried out in the temperature range linear alkanes. It can be said that the packing effect plays a signif-
from T = (318.15 to 358.15) K with intervals of 10 K. In this temper- icant role. In the case of linear compounds, packing is more effec-
ature range, the natural logarithm of c1 13 is a linear function of inverse tive than for the cyclic counterparts, which affects the occurrence
temperature, therefore obtained results can be correlated by linear of stronger solute - solute than IL - solute interactions. In the case
regression, represented by the Eq. (4) with parameters a, b and R2 of cyclic compounds, the interaction between IL and solute is
given in Table 3. Experimental data is presented graphically in Fig. 1. stronger, as evidenced by the lower c1 13 values.
As can be noticed, for different families of hydrocarbons, c1 13 For polar solutes such as alcohols, ketones, acetonitrile, pyridine,
varies in the following order (as an example, the values of c1 13 for
or 1-nitropropan the c1 13 values are definitely lower than for other
compounds with 7 carbon atoms per molecule at 318.15 K are pre- solutes. However, only in the case of methanol, negative deviations
sented in the brackets): n-alkanes (790) > alken-1-enes from ideal behaviour (c1 13 lower than unity) was observed. This is the
(289) > cycloalkanes (201) > alk-1-ynes (44.1) > aromatics (9.81). result of strong IL-solute interactions due to the presence of polar or
The lowest values obtained for aromatic hydrocarbons are associ- associating groups at solutes’ molecules. In turn, for ethers, despite
ated with the possibility of p-p interaction between the aromatic the presence of polar domains in the chemical structure, high values
ring of the solute and the aromatic ring in the imidazolium cation. of c113 were determined. This is undoubtedly related to the presence
The highest c1 13 values were determined for of non-polar chains, which significantly increase these values. The
n-alkanes, which is the result of weak solute–solvent interactions presence of the alkyl chains (from ethyl- to butyl-) causes a signifi-
and confirms very strong positive deviations of the IL-alkane mix- cantly weaker (IL-solute) interaction, which increases c1 13 values.
ture from ideal behavior. Moreover, within a given chemical family Significantly lower c1 13 values were found for cyclic ethers such as
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the value of c1
13 increases with an increase of the alkyl chain length in THF (3.97 at 318.15 K) and dioxane (2.08 at 318.15 K), which is
the solute. At T = 318.15 K, the c113 values for alkanes vary from (790 undoubtedly due to the lack of the steric hindrance and results in
to 1730) for alkanes, from (175 to 268) cycloalkanes, from (289 to a stronger (IL - solute) interaction.
957) for alk-1-enes, or from (14.5 to 76.6) for the tested alk-1- It is interesting to present the influence of the cation structure
ynes. The addition of the CH2 group increases the lipophilicity of of the ionic liquid, especially the presence of functional groups
the solute, which reduces mutual affinity between IL and solute, and the influence of the side chain length in the cation substituent
thus promotes stronger IL-IL interactions. on the c1 13 values and the final effect on the extraction capacity of
The experimental results suggest that the intermolecular inter- IL. It can be discussed based on the comparison of the experimental
actions between the ionic liquid and the solute become stronger results presented here with literature data for [EMIM][SCN] [27],
with an increase in the number of polarizable electrons present [BMIM][SCN] [28], and [HMIM][SCN] [29] with a non-
in double bonds or aromatic rings, probably due to the increasing functionalized alkyl chain. The comparison is graphically presented
strength of ion-induced dipole interactions. in Fig. 2, where the experimental infinite dilution activity coeffi-
The values of c113 for alkanes are higher than the values obtained cients data obtained at T = 318.15 K for different molecular com-
for cycloalkanes, alkenes, alkynes, and aromatic hydrocarbons. The pounds dissolved in [C1C3OHIM][SCN] are collated with those in
introduction of a double or triple bond in the alkanes decreases the [C1Cn=2,4,6IM] [SCN] taken from literature.

Fig. 1. Plot of the experimental infinite dilution activity coefficient (c113 Þ of selected solutes in [C1C3OHIM][SCN] versus temperature (T): (a) n-Alkanes: d, n-heptane; , n-
octane; , n-nonane; , n-decane. (b) Cycloalkanes: d, cyclohexane; , cycloheptane; , cyclooctane; , methylcyclohexane; s, cyclohexene. (c) 1-Alkenes: d, hept-1-
ene; , oct-1-ene; , dec-1-ene. (d) 1-Alkynes: d, pent-1-yne; , hex-1-yne; , hept-1-yne; , oct-1-yne. (e) Aromatic hydrocarbons: d, benzene; , styrene; , toluene;
, alpha-methylstyrene; , o-xylene; , p-xylene; , m-xylene; , ethylbenzene. (f) Alcohols: d, methanol; , ethanol; , propan-1-ol; , propan-2-ol; s, butan-1-ol. (g)
Ethers: d, tetrahydrofuran; , di-n-ethyl ether; , tert-butyl methyl ether; , tert-pentyl methyl ether; , tert-butyl ethyl ether; , di-n-propyl ether; s, di-n-butyl ether.
(h) Ketones: d, acetone; , pentan-2-one; , pentan-3-one; , hexan-2-one; , hexan-3-one. Points – experimental data; Dotted lines – a guide to the eye.
5
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

of the activity coefficients at infinite dilution compared to non-

functionalized [BMIM][SCN]. The same trend was observed in the
previous results for thiocyanate- and dicyanamide- and
tricyanomethanide- based ILs published earlier [43–44]. Because
this trend was observed for ILs with imidazolium, pyrrolidinium,
and morpholinium cation core with different anions like thio-
cyanate, dicyanamide, and tricyanomethanide, it can be speculated
that the effect is independent of both types of the anion as well as
the cation’s core of ILs. Moreover, Fig. 2 shows that the infinite
dilution activity coefficients of different types of molecular com-
pounds decrease with an increase of the alkyl chain length in the
cation substituent.
From the temperature dependence of the infinite dilution activ-
ity coefficients, basic thermodynamic functions such as excess
Gibbs energy, DGE;1
1 , enthalpyDH 1
E;1
and entropy term T ref DSE;1
1 at
infinite dilution were calculated using Eqs. (3) and (5). These val-
ues are collected in Table 4 and graphically presented as a function
of the length of the alkyl chain in Fig. 3.

Table 4
The Partial Molar Excess Gibbs Energies, DGE;1 E;1 E;1
1 , Enthalpies, DH 1 , Entropies, T ref DS1
at Infinite Dilution for the Solutes in [C1C3OHIM][SCN] at the Reference Temperature
Tref = 318.15 K.
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Solutes DGE;1
1 / DHE;1
1 / T ref DSE;1
1 /
kJ∙mol1 kJ∙mol1 kJ∙mol1
n-Heptane 18.06 10.99 7.07
n-Octane 18.92 9.95 8.98
n-Nonane 19.77 8.60 11.16
n-Decane 20.51 7.24 13.27
Cyclohexane 13.73 12.17 1.56
Methylcyclohexane 15.23 11.04 4.19
Cycloheptane 14.19 11.52 2.67
Cyclooctane 15.03 10.91 4.12
Cyclohexene 10.56 6.06 4.50
Hept-1-ene 15.43 7.95 7.48
Oct-1-ene 16.79 7.28 9.52
Dec-1-ene 18.91 6.33 12.58
Pent-1-yne 7.48 0.66 6.82
Hex-1-yne 8.92 1.21 7.71
Hept-1-yne 10.54 1.76 8.78
Oct-1-yne 12.06 2.14 9.92
Benzene 4.76 0.45 4.31
Toluene 6.42 0.08 6.51
Ethylbenzene 8.29 1.24 7.04
o-Xylene 7.55 1.36 6.19
m-Xylene 8.25 0.48 7.76
p-Xylene 8.07 0.86 7.21
Styrene 5.63 0.59 6.22
Alpha-methylstyrene 7.34 1.63 8.98
Methanol 1.07 2.17 3.23
Ethanol 0.92 3.24 2.32
Propan-1-ol 2.13 3.94 1.81
Propan-2-ol 2.34 3.08 0.74
Butan-1-ol 3.43 5.23 1.80
Thiophene 2.99 1.21 4.20
Tetrahydrofuran 3.93 0.24 4.17
1,4-Dioxane 2.23 2.71 4.94
tert-Butyl methyl ether 9.67 2.77 6.91
Fig. 2. The comparison of the infinite dilution activity coefficients (c1
13 Þ of selected tert-Butyl ethyl ether 13.00 5.66 7.34
solutes in thiocyanate-based ILs with imidazolium cations: black bars, [C1C3OHIM] tert-Pentyl methyl 11.10 2.64 8.46
[SCN] (this work); red bars, [EMIM][SCN] [27]; blue bars, [BMIM][SCN] [28]; green ether
bars, [HMM][SCN] [29] at 318.15 K. (For interpretation of the references to colour in Di-n-ethyl ether 9.21 3.69 5.52
this figure legend, the reader is referred to the web version of this article.) Di-n-propyl ether 13.21 5.36 7.85
Di-n-butyl ether 15.93 6.55 9.39
Acetone 2.36 0.82 3.17
The replacement of the methyl group in the cation substituent Pentan-2-one 5.43 0.58 4.85
by the strongly polar hydroxyl group results in a significant Pentan-3-one 5.51 0.37 5.88
Hexan-2-one 6.83 0.17 7.00
increase of the activity coefficients at infinite dilution values for
Hexan-3-one 7.15 0.86 8.01
all solutes tested in this research. For this reason, it can be said that Acetonitrile 0.91 0.34 1.25
strong dipole–dipole interactions between IL cations’ chains due to Pyridine 0.33 3.58 3.91
the presence of polar group may play a significant role and weak- 1-Nitropropane 3.60 0.40 3.99
ens the interaction between functionalized - ionic liquid ([C1C3OH- Standard uncertainties are: u(DGE;1 1 E;1 1
1 ) = ±0.5 kJ∙mol ; u(DH1 ) = ±0.5 kJ∙mol ;
a

IM][SCN]) and solute, which consequently affects the higher values u(T ref DSE;1
1 ) = ±0.05 kJ∙mol 1
.

6
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

strongest exothermic mixing was detected for pyridine

(-3.58 kJmol1), 1,4-dioxane (-2.71 kJmol1), and alpha-
methylstyrene (-1.63 kJmol1). The highest negative values of DH-1
E,1
for these solutes indicate the interactions between cations and/
or anions of the [C1C3OHIM][SCN] and the polar groups in the
solutes are stronger than for other solutes.
The partial excess molar entropies at infinite dilution, TrefDSE,1 1
are positive only for alkanols, which indicate that hydrogen bonds
are breaking during the dissolution process. Negative values of Tref-
DSE,1
1 were observed for other solutes. The negative entropy may
suggest that this particular solute molecule arranges itself in the
IL structure.
To evaluate the proposed IL as a potential extractant, infinite
1
dilution selectivity (S1 12 ) and capacity (k2 Þ were calculated. In gen-
eral, higher values mean better performance of IL when acting as a
separating agent. In this research, [C1C3OHIM][SCN] is considered as
an extractant in the separation of alkanes from aromatics, in the
desulphurization and denitrification of model fuel. For this pur-
pose, the selectivity and capacity values for (heptane/benzene),
(cyclohexane/benzene), (heptane/ thiophene) and (heptane/pyri-
dine) systems were determined using Eqs. (6) and (7). The values
1
of both S1 12 and k2 for IL under study are compared with other ILs
reported in the literature in particular these based on thiocyanate,
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or dicyanamide anions. The summary of this comparison is given in

Table 5 and graphically presented in Fig. 4.
As seen from Fig. 4, the studied IL displays the highest values in
each considered extraction problem among thiocyanate-based ILs.
For SCN-based ILs, the selectivity values in the separation of alka-
nes from aromatics (n-heptane from benzene) decrease in the fol-
lowing order: [C1C3OHIM][SCN] (this work) (S1 12 = 143.6) > [EMIM]
[SCN] [27] (S1 1
12 = 114.7) > [BMIM] [SCN] [28] (S12 = 98.16) > [BMPI
P][SCN] [31] (S12 = 89.47) > [BMPYR][SCN] [30] (S1
1
12 = 79.14) > [BM
Py][SCN] [30] (S1 1
12 = 69.82) > [HMIM][SCN] [29] (S12 = 36.23). The
Fig. 3. Plot of the (a) Excess Gibbs Energy, DGE;1 E;1
1 ; (b) EnthalpyDH1 ; (c) Entropy same sequence was observed for the separation of n-heptane from
term T ref DSE;1 at Infinite Dilution as a Function of Alkyl Chain Length for Organic thiophene, where the highest selectivity value (S1 12 = 280.1) was
1
solutes in [C1C3OHIM][SCN] at T = 318.15 K: , Alkanes; , Cycloalkanes, ,
Alkenes, , Alkynes, , Aromatic Hydrocarbons, , Alcohols, , Ethers. determined for [C1C3OHIM][SCN] and the lowest (S1 12 = 55.04) for
[HMIM][SCN] [29]. As seen in Table 5, the highest S1 12 in separation
of thiophene from heptane is determined for 1-chloroethyl-3-met
The partial molar excess Gibbs free energies are positive for hylimidazolium dicyanamide, [C1C2ClIM] [DCA] [34] (S1 12 = 351),
most of the solutes excepting methanol. For different families of 1-hydroxypropyl-3-methyl-imidazolium thiocyanate, [C1C3OHIM]
hydrocarbons, DGE;1
1 , varies in the following order (as an example,
[SCN] (this work) (S1 12 = 280.1) and 1-hydroxyethyl-3-methyl-imi

the values of DGE;1 in kJmol1, for compounds with 7 carbon dazolium dicyanamide, [C1C2OHIM][DCA] [34] (S1 12 = 270.5) and
1
atoms per molecule are given in the brackets): n-alkanes (18.06) the lowest for 1-hexyl-3-methyl-imidazolium thiocyanate,
> alken-1-enes (15.43) > cycloalkanes (14.19) > alk-1-ynes (10.54 [HMIM][SCN] [29] (S1 12 = 55.04).

) > aromatics (6.42). The highest values of the DGE,1 1 for n- The functionalization of IL’s cation with hydroxyl group results
alkanes confirmed that the interaction between ionic liquid and in a significant increase in selectivity: 1.46 times for n-heptane/
aliphatic hydrocarbons is very weak. The significantly lower values benzene, 1.65- times for n-heptane/thiophene, and 1.46- times
were determined for aromatic hydrocarbons and the cause was for cyclohexane/benzene separations. This trend was also con-
discussed based on the measured c1 firmed for dicyanamide-based IL with pyrrolidinium- [36],
13 values. Due to the presence
of delocalized electrons and the ability to form hydrogen bonds pyridinium- [36], or imidazolium cation [33,34]. Furthermore,
with IL, the lowest values of the DGE,1 1 were determined for the comparison between [C1C3OHIM][SCN] and [C1C3OHIM][DCA]
alcohols (from 1.07 kJmol1 for methanol to 3.43 kJmol1 for shows that in each considered extraction problem, the selectivity
butan-1-ol), pyridine (0.33 kJmol1), acetonitrile (0.91 kJmol1), values of the IL proposed in this work are much higher. For exam-
1,4-dioxane (2.23 kJmol1), acetone (2.36 kJmol1) and thiophene ple, S112 the for the heptane/benzene system is 143.6 and 101.4 for
(2.99 kJmol1). [C1C3OHIM][SCN] and [C1C3OHIM][DCA] [33], respectively. It is
For a great majority of solutes, DHE;1 > 0, which means that worth mentioning that [C1C3OHIM][SCN] exhibits an extremely
1
mixing with the ILs would result in the absorption of heat. The high selectivity value of separation of n-heptane from pyridine
higher values of DHE,1 were observed for the alkanes, cycloalka- (S1 1
12 = 759.6). So far, the highest S12 values in the separation of
1
nes, and alkenes than for other solutes under work. In general, an nitrogen compounds from fuels have been reported for DCA- based
increase of the alkyl chain length in the solute results in a decrease IL, namely: (3-cyanopropyl)-4-methyl-pyridinium dicyanamide,
of DHE,1 varies from 10.99 kJmol1 for n- [C3CNPy][DCA] [36] (S1 12 = 394.4) and N-hydroxypropylpyridinium
1 . For example, DH1
E,1
1
heptane to 7.24 kJmol for n-decane. The negative values of the dicyanamide, [C3OHPy][DCA] [46] (S1 12 = 346.0). Such high selectiv-

DHE,1
1 were determined for the following solutes: toluene, styrene, ity values provide promising information about the possibility of
alpha-methylstyrene, thiophene, tetrahydrofuran, 1,4-dioxane, using the proposed ionic liquid in the presented extraction
ketones, acetonitrile, pyridine, and nitropropane. However, the processes.

7
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554
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Fig. 4. (a) The comparison of the selectivity (S1 12 ) at infinite dilution for different separation problems at T = 318.15 K: black bars, (n-heptane / benzene); red bars,
1
(cyclohexane / benzene); blue bars, (n-heptane / thiophene); green bars, (heptane / pyridine); (b) The comparison of the capacity (k2 Þat infinite dilution for different
separation problems at T = 318.15 K: black bars, benzene; red bars, thiophene; blue bars - pyridine. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

Table 5
1
Selectivities, S1
12 and Capacities, k2 for Different Separation Problems for Imidazolium-, or Thiocyanate-based Ionic Liquids at T = 318.15 K.

S1
12
1
k2

heptane/benzene cyclohexane /benzene heptane/thiophene heptane/pyridine benzene thiophene pyridine

[EMIM][SCN] [27] 114.7 26.95 – – 0.29 – –
[BMIM][SCN] [28] 98.16 21.71 169.6 – 0.46 0.80 –
[HMIM][SCN] [29] 36.23 12.16 55.04 – 0.50 0.76 –
[C1C3OHIM][SCN] (this work) 143.6 31.82 280.1 759.6 0.18 0.35 0.96
[BMPy][SCN] [30] 69.82 18.22 118.0 – 0.59 1.00 –
[BMPYR][SCN] [30] 79.14 19.49 138.3 – 0.53 0.93 –
[BMPIP][SCN] [31] 89.47 21.00 154.6 – 0.53 0.91 –
[BMIM][DCA] [32] 48.66 13.80 79.82 107.7 0.53 0.88 1.18
[C1C3OHIM][DCA] [33] 101.4 22.20 183.2 336.1 0.23 0.41 0.75
[C1C2OHIM][DCA] [34] 146.5 25.05 270.5 – 0.20 0.37 –
[C1C2ClIM][DCA] [34] 181.9 36.61 351.0 – 0.17 0.33 –
[BMPy][DCA] [35] – – 98.10 – – 1.18 –
[C3CNPy][DCA] [36] 126.6 31.43 256.4 394.4 0.16 0.33 0.51
[C3OHPy][DCA] [45] 95.82 20.92 185.0 346.0 0.20 0.38 0.72
[BMPYR][DCA] [37] 53.90 14.96 89.31 – 0.71 1.18 –
[C1C3CNPYR][DCA] [36] 128.9 28.89 246.8 313.5 0.28 0.53 0.68

8
 M. Królikowski, M. Królikowska and C. Markowski J. Chem. Thermodynamics 161 (2021) 106554

Unfortunately, high selectivity results in a very low capacity, Acknowledgment

which is shown in Fig. 4. IL proposed here displays one of the low-
1
est values of k2 thus, the practical extraction performance of this IL This work has been funded by The Warsaw University of
is greatly limited. The capacity values are 0.18 for benzene, 0.35 for Technology.
thiophene and 0.96 for pyridine. Among thiocyanate- based ILs, the
1
k2 for thiophene decreases in the following series: [BMPy][SCN] Appendix A. Supplementary data
1 1
[30] (k2 = 1.00) > [BMPYR][SCN] [30] (k2 = 0.93) > [BMPIP][SCN]
1 1
[31] (k2 = 0.91) > [BMIM][SCN] [28] (k2 = 0.80) > [HMIM][SCN] Supplementary data to this article can be found online at
1 1
[29] (k2 = 0.76) > [C1C3OHIM][SCN] (this work) (k2 = 0.35). Chang- https://doi.org/10.1016/j.jct.2021.106554.
ing IL’s anion from thiocyanate to dicyanamide results in an
1
increase in k2 for benzene and thiophene but a decrease for pyri- References
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CRediT authorship contribution statement
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