J. Chem.

Thermodynamics 41 (2009) 13031311

Contents lists available at ScienceDirect

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

Phase equilibria study of the binary systems (ionic liquid + thiophene): Desulphurization process
Urszula Domanska *, Marek Krlikowski, Katarzyna Slesinska
Warsaw University of Technology, Laboratory of Applied Thermodynamics, Faculty of Chemistry, Physical Chemistry Department, Noakowskiego 3, 00-664 Warsaw, Poland

a r t i c l e

i n f o

a b s t r a c t
(Solid + liquid) equilibria (SLE) and (liquid + liquid) equilibria (LLE) for the binary systems: {ionic liquid (IL) N-butyl-4-methylpyridinium tosylate (p-toluenesulfonate) [BM4Py][TOS], or N-butyl-3methylpyridinium tosylate [BM3Py][TOS], or N-hexyl-3-methylpyridinium tosylate [HM3Py][TOS], or N-butyl-4-methylpyridinium bis{(triuoromethyl)sulfonyl}imide [BM4Py][NTf2], or 1,4-dimethylpyridinium tosylate [M1,4Py][TOS], or 2,4,6-collidine tosylate [M2,4,6Py][TOS], or 1-ethyl-3-methylimidazolium thiocyanate [EMIM][SCN], or 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or 1-hexyl-3methylimidazolium thiocyanate [HMIM][SCN], or triethylsulphonium bis(triuoromethylsulfonyl)imide [Et3S][NTf2] + thiophene} have been determined at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from (270 to 390) K. In the case of systems (pyridinium IL, or sulphonium IL + thiophene) the mutual immiscibility with an upper critical solution temperature (UCST) was detected at the very narrow and low mole fraction of the IL. For the binary systems containing (imidazolium thiocyanate IL + thiophene), the mutual immiscibility with the lower critical solution temperature (LCST) was detected at the higher mole fraction range of the IL. The basic thermal properties of the pure ILs, i.e. melting and glass-transition temperatures as well as the enthalpy of fusion have been measured using a differential scanning microcalorimetry technique (DSC). The well-known NRTL equation has been used to correlate experimental SLE/LLE data sets. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 20 May 2009 Accepted 5 June 2009 Available online 9 June 2009 Keywords: Pyridinium ionic liquid Imidazolium ionic liquids Sulphonium ionic liquid (Solid + liquid) phase diagrams (Liquid + liquid) phase diagrams Thermodynamics

1. Introduction Ionic liquids (ILs) form a novel class of chemical compounds with interesting properties that are driving new research in many elds. Their specic properties, i.e. broad temperature range of liquid phase existence, extremely low vapour pressure, air and moisture stability, and high extraction potential make ILs interesting from the point of view of potential applications in desulphurization process of diesel fuel [112]. Knowledge of the phase equilibria {(solid + liquid) equilibria, SLE and (liquid + liquid) equilibria, LLE} are fundamental for the ILs to be effectively used as solvents in liquidliquid extraction [1315]. Until recently, according to the necessarily deep desulphurization of diesel fuel, the most important and popular imidazolium ILs were considered as extractive solvents: [BMIM]Cl/AlCl3 (0.35/ 0.65) [1], [BMIM][OcSO4] [2], [EMIM][BF4], [BMIM][BF4] [3], [OcMIM][BF4] [5,9], [OcMIM][NTf2] [68], and [EMIM][EtSO4] [10]. It was observed by Holbrey et al. [11] that dimethylpirydinium ILs, as N-butyl-2,4-dimethylpyridinium, or N-butyl-2,5-dimethylpirydinium bis{(triuoromethyl)sulfonyl}imide have shown

* Corresponding author. Tel.: +48 22 6213115; fax: +48 22 6282741. E-mail address: ula@ch.pw.edu.pl (U. Domanska). 0021-9614/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.jct.2009.06.003

much greater extraction potential than other ionic liquids. While aliphatic hydrocarbons are poorly soluble in many ionic liquids [15], the positive extraction results reveal from the high model sulphur compound (thiophene) solubility in the IL. It was proved by Domanska and Laskowska [16] by the measurements of the activity coefcient at innite dilution, c1 and by Holbrey et al. [11] that 13 the thiocyanate anion [SCN] has high extraction efciency. The 1 selectivities Sij c1 =c1 for the hexane/thiophene, heptane/thioi3 j3 phene, separation problems were calculated for [BMIM][SCN] from the c1 . The selectivities at T = 298.15 K are 186.2 and 231.5, 13 1 respectively. The capacity kj 1=c1 for the sulphur (thiophene) j3 separation is 0.82, which is quite high. These are very promising results for the separation of sulphur from mixtures of industrial importance. According to the new regulations, reneries have to reduce sulphur level for liquid fuels in the USA and in Europe. The selectivity of alkane/thiophene separation increases with an increase of the alkane chain, and decreases with an increase of temperature. The highest value of selectivity S1 517:3 was obij served for decane/thiophene at T = 298.15 K [16]. It is possible to make some comparisons between different ILs used in this separation problem from the ternary (liquid + liquid) equilibrium, LLE. Using [OcMIM][BF4], the highest value of selectivity of separation for hexane/thiophene at T = 298.15 K is 18.69 [5], or for [OcMIM][Tf2N] 7.55 [7].

1304

U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311

The intermediate results were obtained by us earlier for 1-butyl3-methylimidazolium triuoromethanesulfonate [BMIM][CF3SO3] at T = 298.15 K from the measurements of the activity coefcients. For hexane/thiophene, this value was: 36.5 [17]. Interesting results for the hexane/thiophene separation at T = 298.15 K were obtained also from the activity coefcient measurements for triethylsulphonium bis{(triuoromethyl)sulfonyl}imide [Et3S][NTf2] [18], 1-butyl-1-methylpyrrolidinium triuoromethanesulfonate, [BMPYR][CF3SO3] [19], and N-butyl-4-methylpyridinium bis{(triuoromethyl)sulfonyl}imide [BM4Py][NTf2] [20], which were 30.9, 70.1 and 25.2, respectively. Interestingly, most of the calculated results relate to the activity coefcient at innite dilution measurements [1621]. The very high sulphur extraction potential reveals n-acryloxypropyl-N-methylimidazolium bromide, [APN-MIM]Br at T = 298.15 K, which is 85.3 (value extrapolated to innity) [21] in comparison with [BMIM][SCN], S1 186 [16]. As we observed, ij the thiocyanate [SCN] anion has attracted attention. The results of extraction for aromatic compounds, because of similarity of the structure with thiophene, are of little use in solvent extraction processes for separating aromatic compounds from thiophene. Also, recently published results for the vapour pressure of binary mixtures of two ILs ([BMIM][PF6] and [BMIM][BF4]) with benzene, or thiophene, has shown signicant similarity of systems with benzene and thiophene [22]. Ionic liquids can depress the volatility of aromatic compounds to a high degree. Usually, SLE and LLE of binary or ternary systems containing the IL and different organic solvents have been measured [1315]. The properties of the ILs can be designed by the use of different selected combinations of anions and cations. By changing these features of the ILs, the physicochemical properties, the phase equilibria, and extraction possibilities for different separation problems are affected. This paper is a continuation of our wide ranging investigation into ILs containing the varying cation (pyridinium, imidazolium, and sulphonium) and with a range of anion types (tosylate, bis{(triuoromethyl)sulfonyl}imide and thiocyanate anions). Determination of activity coefcients at innite dilution of organic solutes in the ionic liquid, N-butyl-4-methylpyridinium tosylate ([BM4Py][TOS]) by gasliquid chromatography (GLC) has been reported earlier [23]. The moderate selectivity values indicated that this ionic liquid is not the best for solvent extraction processes in separating aromatic compounds from aliphatic compounds. Nevertheless, the tosylate anion as a polyaromatic anion leads to high solubility of polyaromatic sulphur compounds. However, the tosylate-based ionic liquids are technically limited by their higher melting temperatures. Usually, better results are observed for the peruorinated anions, such as bis{(triuoromethyl)sulfonyl}imide. The conductor-like screening model (COSMO-RS) was recently used to test 24 anions and 11 cations in 264 possible combinations as potential solvents for the removal of aromatic sulphur compounds from diesel oil by the LLE extraction [24]. It was found for the removal of thiophene that the smaller size of the cations yielded the maximum selectivity and that the imidazolium cation, because of its similar structure with thiophene gave better selectivity than pyridinium, or quinolinum cations [24]. It was noted from the calculated results that the thiocyanate anion can be quite important in this selection of entrainers [24]. The purpose of this work is to present the solubility of many ionic liquids as: N-butyl-4-methylpyridinium tosylate (p-toluenesulfonate) [BM4Py][TOS], or N-butyl-3-methylpyridinium tosylate [BM3Py][TOS], or N-hexyl-3-methylpyridinium tosylate [HM3Py] [TOS], or N-butyl-4-methylpyridinium bis{(triuoromethyl)sulfonyl}imide [BM4Py][NTf2], or 1,4-dimethylpyridinium tosylate [M1,4Py][TOS], or 2,4,6-collidine tosylate [M2,4,6Py][TOS], or 1-ethyl-3-methylimidazolium thiocyanate [EMIM][SCN], or 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or

1-hexyl-3-methylimidazolium thiocyanate [HMIM][SCN], or triethylsulphonium bis(triuoromethylsulfonyl)imide [Et3S][NTf2] in thiophene. We believe it is possible to get more information about the selectivity potential of extraction of polyaromatic sulphur compounds from diesel fuel from the data of solubility in binary systems.

2. Experimental 2.1. Materials The ILs N-butyl-4-methylpyridinium tosylate (p-toluenesulfonate) [BM4Py][TOS], or N-butyl-3-methylpyridinium tosylate [BM3Py][TOS], or N-hexyl-3-methylpyridinium tosylate [HM3Py] [TOS], or N-butyl-4-methylpyridinium bis{(triuoromethyl)sulfonyl}imide [BM4Py][NTf2], were synthesized for us by request by IoLiTec Ionic Liquids Technology GmbH, Germany and were reported to have a mass fraction purity of >0.98. The 1,4-dimethylpyridinium tosylate [M1,4Py][TOS], and 2,4,6-collidine tosylate [M2,4,6Py][TOS] were supplied by SigmaAldrich Chemie GmbH, Steinheim, Germany. The ILs 1-ethyl-3-methylimidazolium thiocyanate [EMIM][SCN], or 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or 1-hexyl-3-methylimidazolium thiocyanate [HMIM][SCN] were supplied by Fluka. Triethylsulphonium bis(triuoromethylsulfonyl)imide [Et3S][NTf2] was supplied by Solvent Innovation. Thiophene was supplied by SigmaAldrich Chemie GmbH, Steinheim, Germany. The ionic liquids were puried by subjecting the sub-cooled liquid to a very low pressure of about 5 103 Pa at a temperature about 300 K for approximately 5 h. Thiophene was fractionally distilled before use over drying reagent to achieve mass fraction purity P0.998. It was stored over freshly activated molecular sieves of 4 1010 m (type 4 Union Carbide) and checked by gasliquid chromatography (GLC). The list of ionic liquids investigated in this work is presented in table 1. 2.2. Differential scanning microcalorimetry The basic thermal characteristics of the ionic liquids, i.e. temperature of fusion (Tfus,1), enthalpy of fusion (DfusH1), glass-transition temperature (Tg,1), and change of heat capacity at the glass-transition temperature, Tg,1 (DCp(g),1) have been measured using a differential scanning microcalorimetric technique (DSC). The applied scan rate was 5 K min1, with a power and recorder sensitivities of 16 mJ s1 and 5 mV, respectively. The apparatus (PerkinElmer Pyris 1) was calibrated with a 0.999999 mol fraction purity indium sample. The average value of the melting temperature was (Tfus,1 0.05) K averaged over four scans. The repeatability of that value was 0.05 K, and was comparable to the visual measurement. The enthalpy of fusion was (DfusH1 0.08) kJ mol1 and the Tg,1 (Tg,1 0.1) K with (DCp(g),1 3) J mol1 K1. The molar masses and the thermophysical properties are shown in table 2. 2.3. Density measurements The densities of the liquid ionic liquids were measured using an Anton Paar GmbH 4500 vibrating-tube densimeter (Graz, Austria), thermostated at different temperatures. Two integrated Pt(1 0 0) platinum thermometers provided good precision for internal temperature control (T 0.01 K). The densimeter includes an automatic correction for the viscosity of the sample. The apparatus is precise to within 1 105 g cm3, and the uncertainty of the measurements was estimated to be better than 5 105 g cm3. The calibration of the densimeter was performed at atmospheric pressure using doubly distilled and degassed water, specially puried

 U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311 TABLE 1 List of ionic liquids investigated in this work. N-Butyl-4-methylpyridinium tosylate

1305

O CH3 O S

[BM4Py][TOS]

C4H9
N-Butyl-3-methylpyridinium tosylate

CH3 O O CH3 S
-

[BM3Py][TOS]

C4H9

CH3

N-Hexyl-3-methylpyridinium tosylate

O O CH3 N
+

[HM3Py][TOS]

C6H13

CH3

N-Butyl-4-methylpyridinium bis{(triuoromethyl)sulfonyl}imide

CH3 O F N
+

[BM4Py][NTf2]

N S

O S F F F

C4H9

O
1,4-Dimethylpyridinium tosylate

CH3

[M1,4Py][TOS]

CH3

CH3 O
-

2,4,6-Collidine tosylate

CH3

[M2,4,6Py][TOS]

H3C

N H

CH3 CH3
(continued on next page)

1306 TABLE 1 (continued) 1-Ethyl-3-methylimidazolium thiocyanate

U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311

H3C N
1-Butyl-3-methylimidazolium thiocyanate

[EMIM][SCN]

C2H5 S
-

C
+

[BMIM][SCN]

H3C N
1-Hexyl-3-methylimidazolium thiocyanate

C4H9 S
-

[HMIM][SCN]

H 3C N
Triethylsulphonium bis(triuoromethylsulfonyl)imide

C6H13 S
-

[Et3S][NTf2]

S O F F F S O

O S O F F F

TABLE 2 The molar mass, molar volume, and thermophysical constants of pure ionic liquids, determined from DSC data. Compound [BM Py][TOS] [BM3Py][TOS] [HM3Py][TOS] [BM4Py][NTf2] [M1,4Py][TOS] [M2,4,6Py][TOS] [EMIM][SCN] [BMIM][SCN]c [HMIM][SCN] [Et3S][NTf2]
a b c 4 a

M (g mol1) 321.43 321.43 349.49 430.39 279.35 293.38 169.25 197.30 211.33 399.39

Vm (cm3 g1) 288.8 288.8b 321.0b 304.8 240.5b 234.4b 151.5 184.4 199.9 273.6
b

Tfus,1 (K) 324.8 323.7 329.3 291.4 424.8 403.7

DfusH1 (kJ mol1)

14.33 1.533 10.094 21.94 30.89 22.88

Ttr,1 (K) 215.8 (g) 220.1 (g) 234.0(g) 195.9 (g) 265.3 (g) 175.6 (g) 181.6 (g) 189.9 (g) 241.1; 199.3 (g)

DtrH1 (kJ mol1)

DCp(g),1 (J mol1K1)
153 136 117 149 113 97.9 97.7 118 59.5

262.8

6.98

9.41

From reference [25]. Calculated as for a hypothetical sub-cooled liquid by the group contribution method described by Barton [26]. From reference [16].

benzene (CHEMIPAN, Poland 0.999), and dried air. Mixtures were prepared by weighing; the error in mole fraction being estimated as less than 5 104. The results as molar volumes of the ILs are presented with other physicochemical properties in table 2. 2.4. Phase equilibria apparatus and measurements A dynamic (synthetic) method for the solubility measurements was used in the present work. Details of the procedures have been described previously [27]. The ionic liquids were kept under nitrogen in a dry-box during the short time of adding the solvent to the vessel. (IL + thiophene) were prepared by weighing the pure com-

ponents with uncertainty of 1 104 g. Mixtures were prepared by mass, and errors did not exceed 5 104 in mole fraction. The sample was heated very slowly (<2 K h1) with continuous stirring inside a Pyrex glass cell placed in a thermostat. The crystal disappearance temperatures, detected visually, were measured with an electronic thermometer P 550 (DOSTMANN electronic GmbH) with the probe totally immersed in the thermostatting liquid. The uncertainties of the temperature measurements were judged to be 0.05 K. The repeatability of the SLE/LLE experimental points was 0.05 K. The results of the solubility measurements are listed in table 3, where the direct experimental results of the SLE equilibrium temperatures, TSLE and of the LLE equilibrium

 U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311 TABLE 3 Experimental (solid and liquid + liquid) phase equilibrium in the {IL (1) + thiophene (2)} binary systems. x1 1.0000 0.9980 0.9693 0.9428 0.9061 0.8584 0.8384 0.8046 0.7834 0.7652 0.7298 0.6976 0.6645 1.0000 0.9797 0.9323 0.8925 0.8583 0.8271 0.7951 0.7393 0.6893 0.6470 0.6105 0.5754 0.5433 0.4813 0.1729 1.0000 0.9175 0.8534 0.8066 0.7578 0.7125 0.6759 0.6145 0.5608 0.5173 0.4787 0.4455 0.4173 0.3949 0.3753 0.3408 0.3117 0.2757 0.1427 0.1402 0.1375 0.1340 0.1295 0.1260 0.1227 0.1201 0.1177 0.1154 0.1122 0.1097 0.1068 0.1029 1.0000 0.6218 0.5639 0.5262 0.4877 0.4566 0.4097 424.8 410.7 407.8 404.9 402.4 399.1 394.0 TSLE/K 324.8 323.5 322.3 320.9 318.9 315.9 314.7 313.5 312.2 311.2 309.3 307.5 305.2 [BM3Py][TOS] 323.7 322.9 319.7 317.9 316.6 315.3 313.6 309.8 306.3 303.2 300.1 298.5 295.5 292.4 285.8 [HM3Py][TOS] 329.3 327.1 325.3 324.3 322.5 320.6 318.8 316.0 312.4 310.7 309.0 307.1 304.9 303.0 301.2 297.6 293.2 288.0 0.2462 0.2177 0.1874 0.0431 0.0423 0.0404 0.0354 0.0302 0.0254 0.0218 0.0189 0.0167 0.0150 0.0132 0.0114 0.0100 0.0088 [BM4Py][NTf2] 269.0 0.0010 278.0 0.0009 287.6 0.0007 298.5 0.0007 308.9 0.0006 317.7 0.0006 323.6 0.0005 330.6 0.0004 337.1 0.0003 342.4 0.0003 348.3 0.0003 355.4 0.0002 364.1 367.6 [M1,4Py][TOS] 0.2596 0.2472 0.2444 0.2419 0.2393 0.2364 0.2341 379.1 378.4 377.9 389.5 400.6 412.3 421.0 280.4 273.6 268.4 294.6a 295.8a 297.0a 298.7a 300.2a 301.0a 301.3a 301.7a 301.5 300.6 299.4 297.6 295.2 293.5 0.1705 0.1687 0.1670 0.1654 0.1637 0.1622 0.1607 0.1595 0.1580 0.1567 0.1555 0.1543 0.1531 0.1520 296.8 306.0 313.0 317.3 322.6 326.0 330.2 334.5 338.4 341.5 345.0 348.9 351.7 355.5 TLLE/K [BM4Py][TOS] 0.6339 0.5839 0.5606 0.5143 0.4793 0.4471 0.4219 0.3778 0.3429 0.3082 0.2786 0.2521 303.3 299.5 297.5 293.4 289.9 286.9 284.8 281.7 279.8 277.1 274.9 272.6 x1 TSLE/K TLLE/K TABLE 3 (continued) x1 0.3746 0.3374 0.2871 1.0000 0.5056 0.3545 0.3010 0.2505 0.1930 0.1554 0.1379 0.1256 0.1172 0.1060 0.0990 0.0892 0.0821 0.0767 0.0640 0.0591 0.0520 0.0411 0.0386 0.0349 0.3795 0.3750 0.3708 0.3665 0.3629 0.3601 0.3525 0.3479 0.3429 0.3376 0.3323 0.3246 0.3210 0.3171 0.2542 0.2520 0.2493 0.2470 0.2437 0.2404 0.2389 0.2356 0.2317 0.2300 0.2281 0.2250 0.2233 0.2211 0.2191 0.1640 0.1625 0.1607 0.1585 0.1553 0.1456 0.1453 0.1999 0.1959 0.1921 0.1910 0.1901 0.1880 0.1863
a

1307

TSLE/K 389.3 385.6 381.5 403.7 347.3 317.2 310.0 305.8 301.9 299.1 298.2 298.0 297.7 297.8 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7

TLLE/K

x1 0.1940 0.1517 0.1192

TSLE/K 377.8 377.8 377.8 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.7 297.4 295.1 293.9 293.4 293.2

TLLE/K

[M2,4,6Py][TOS] 0.0344 0.0315 0.0277 0.0263 0.0246 0.0341 0.0229 0.0212 0.0201 0.0196 0.0168 0.0145 0.0140 0.0090 299.8 0.0054 303.5 0.0042 306.3 0.0029 308.1 0.0024 311.0 0.0021 312.1 0.0018 313.5 355.3 351.1 347.8 344.2 341.6 338.0 334.3 330.2 326.0 321.2 317.6 309.9 306.7 303.9 354.0 349.4 341.2 332.9 326.2 320.5 315.3 310.3 303.3 301.5 299.4 295.8 291.6 287.2 281.5 364.7 362.5 355.4 352.4 346.5 320.6 333.4 251.8 273.7 284.8 291.4 297.2 305.7 313.8 [EMIM][SCN] 0.3147 0.3094 0.3031 0.2967 0.2942 0.2881 0.2878 0.2812 0.2757 0.2663 0.2585 0.2462 0.2388 [BMIM][SCN] 0.2152 0.2145 0.2048 0.1981 0.1947 0.1921 5.28 104 3.62 104 3.44 104 3.26 104 3.06 104 3.06 104 3.26 104 3.44 104 3.62 104 [HMIM][SCN] 0.1426 0.1413 0.1395 0.1376 0.1367 0.1341 [Et3S][NTf2] 0.1860 0.1850 0.1837 0.1824 0.1812 0.1796

313.5 314.6 314.8 314.6 314.4 314.2 314.0 313.9 313.4 313.4 312.4 311.7 311.3 307.1

301.5 296.8 291.1 287.1 283.6 279.1 278.2 271.6 265.8 257.8 251.6 242.9 236.6

345.5a 333.3a 321.2a 320.4a 319.9a 314.0a 309.3a 299.2a 293.1a 290.2a 282.8a 277.3a

271.9 274.6 262.6 249.8 244.7 233.0 341.1a 319.9a 313.3a 308.1a 303.3a 285.3a 283.9a 282.5a 281.4a 303.8 290.8 279.1 265.8 253.3 247.8

312.8 323.4 333.4 341.2 349.0 356.7

Thiophene rich phase.

1308

U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311

temperatures, TLLE versus ionic liquid mole fraction, x1 for the system (IL + thiophene) are shown. The visual method was not applicable at very low mole fraction of the IL (x1 = 1 105) mainly because of uncertainties and verticality of the saturated equilibrium curve, thus only for three systems the solubility curve at thiophene rich mixtures were detected.

380

350

Water content was analyzed by KarlFisher titration (method TitroLine KF). Samples of ILs and the thiophene were dissolved in dry methanol and titrated with steps of 2.5 106 dm3. The analysis showed that the water mass fraction in the solvents and in the mixtures with the ionic liquid, were <260 106. 3. Results and discussion The six p-delocalized electrons in aromatics (thiophene) can strongly interact with the polar cation and/or anion of the ionic liquid. All tosylate-based ILs under investigation reveal high interaction with thiophene, because only in the very narrow area at the thiophene rich phase the immiscibility in the liquid phase was observed (see for example gure 1 for [M1,4Py][TOS]). The interaction is mainly due to pp interactions between benzene ring of the tosylate anion of the IL and of the thiophene. The comparison between [BM4Py][TOS] and [BM3Py][TOS] is difcult to discuss because we could not determine the immiscibility curve for [BM4Py][TOS]. The melting temperatures are very close to each other, thus the liquidus curves are almost the same. The comparison between [BM3Py][TOS] and [HM3Py][TOS] shows lower solid solubility of [HM3Py][TOS], because of the higher melting temperature. The liquidus curve is a few degree higher for [HM3Py] [TOS], but the immiscibility in the liquid phase exists in the lower mole fraction of the IL. The immiscibility gap for [BM3Py][TOS] lies between 0 and 0.2 mole fraction of the IL and for [HM3Py][TOS] it can be expected to lie between 0 and 0.1 mole fraction of the IL. Also, the Upper Critical Solution Temperature, UCST is lower for the [HM3Py][TOS] (301.7 K) than for [BM3Py][TOS] (>356 K). The comparison between [BM4Py][TOS] and [BM4Py][NTf2] shows completely different phase diagrams. The [NTf2] anion as usual

T /K

2.5. Water content

320

290

260

230 0 0.2 0.4

X1

0.6

0.8

FIGURE 2. Plot of temperature against mole fraction to illustrate the experimental (liquid + liquid) equilibria of binary system {[BM4Py][NTf2] (1) + thiophene (2)}. The corresponding solid lines represent correlation by means of the NRTL equation.

decreases the melting temperature of the IL (see table 2), which is liquid at room temperature and reveals only the immiscibility in the liquid phase between the 2 104 and 0.14 mole fraction of the IL with the UCST (>370 K). Thus the complete miscibility is observed above 0.14 mole fraction of the IL (see gure 2). Three systems with [EMIM][SCN], [BMIM][SCN], and [HMIM][SCN] show the value of the Lower Critical Solution Temperature, LCST in mixtures with thiophene as it was observed in the solubility of thiocyanate-based ILs with aromatic hydrocarbons [28]. However, from the few experimental points in the system ([BMIM][SCN] + thiophene) in the thiophene rich side, we can conclude that a similar result can be expected in these systems for the LCST and the UCST points. The solubility of these three ionic liquids is presented as the LLE temperature versus mole fraction plot of the IL in gure 3. The solubility increases (the area of miscibility decreases) when the alkane chain at the cation

440

380 350

420

320
350

T /K

T /K

260
380

230 200 0
0 0.2 0.4

T /K

400

290

330 310 290 270 0 0.4 0.8 1.2 1.6 3 10 X 1 2

360

0.2

0.4

0.6

0.8

X1

0.6

0.8

X1
FIGURE 3. Plot of temperature against mole fraction to show the experimental (liquid + liquid) equilibria of binary systems {IL (1) + thiophene (2)}: 4, [EMIM][SCN]; j, [BMIM][SCN]; s, [HMIM][SCN]. The corresponding solid lines represent correlation by means of the NRTL equation.

FIGURE 1. Plot of temperature against mole fraction to show the experimental (solid + liquid) equilibria of binary system {[M1,4Py][TOS] (1) + thiophene (2)}. The corresponding solid lines represent correlation by means of the NRTL equation.

 U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311 TABLE 4 Results of correlation of the experimental (solid + liquid) equilibrium data of different ionic liquids with thiophene binary systems by means of the NRTL equation, (a = 0.5): obtained values of parameters and root-mean-square deviations (RMSD) of temperature (rT). Ionic liquid

1309

Dg12/(J mol1) Dg21/(J mol1)

NRTL parameters 298.02 2222.98 5804.62 780.70 5001.40 1347.69

rT/(K)

[B3MPy][TOS] [H3MPy][TOS] [M1,4MPy][TOS]

1.10 1.47

The maximum of the binodal curves for ([BM4Py][NTf2], or [EMIM][SCN], or [BMIM][SCN], or [HMIM][SCN] and [Et3S][NTf2] + thiophene) binary mixtures is at very high temperatures and it was impossible to measure them in water, or in an oil bath using the static method. Generally for the trend observed in the solubility of thiophene in the ILs, the consolute temperatures of LLE are at very low mole fraction of the IL and are mostly undetectable with the visual method. 4. Modelling

1.58

4.1. Correlation of (solid + liquid) equilibrium Since no solidsolid phase transitions were observed in this work (excluding [Et3S][NTf2]), and the change of heat capacity at the melting temperature was not measured, a simplied general thermodynamic equation relating temperature, TSLE and the mole fraction of the IL, x1 in thiophene have been tted to all the sets of experimental SLE results [30]:

increases. It was earlier observed for two of these systems ([EMIM][SCN] and [BMIM][SCN]) from the values of activity coefcients and the partial molar excess enthalpies at innite dilution DHE;1 values from the activity coefcients at innite dilution meal surements that the interaction with thiophene has the same order [16,29]. Complete miscibility in the liquid phase was observed for [HMIM][SCN] up to 0.14 mole fraction of the IL at T = 300 K. This is a comparable result to the [BM4Py][NTf2] ionic liquid. As we expected, thiophene interacts very strongly with the sulphonium-based IL. In this case, the major inuence on solubility has very strong interactions between the S atom of the IL cation and/or [NTf2] anion and the sulphur atom in thiophene. Usually, the selectivity of n-alkane/thiophene separation calculated from the activity coefcients at innite dilution measurements decreases with an increase of temperature. From our solubility measurements, it is not so obvious, because the solubility curve (LLE) is quite vertical at the IL rich phase (see table 3). The complete miscibility in the liquid phase is observed up to about 0.2 mole fraction of the IL. On the basis of the phase diagrams investigated for the systems (IL + thiophene), the following trends can be seen: simple eutectic systems may be expected with the eutectic point shifted to the very low mole fraction of the IL (see gure 1); the solubility of the solid IL in thiophene decreases as the length of carbon chain of the pyridinium cation increases, the LLE curves show opposite effects; solubility of the IL in thiophene decreases as the melting temperature of the pyridinium IL increases (the melting temperature of [M1,4Py][TOS] is the highest). In the case of thiocyanate-based ILs, the solubility of thiophene in the IL increases with increasing carbon chain at the cation. This is unquestionably the inuence of the cation of the IL on its phase behaviour with the same solvent. Replacing the anion [TOS] with [NTf2] changes the nature of the IL from solid to liquid at room temperature and shows the LLE phase diagram. New data reveal complete miscibility in the liquid phase from low to high temperatures over a wide range of mole fraction of the IL.

ln x1

  Dfus H1 1 1 ln c1 ; R T SLE T fus;1

where Tfus,1, DfusH1, TSLE, x1, and c1 stand for: melting temperature for the pure IL, enthalpy of fusion for the pure IL, (solid + liquid) equilibrium temperature, equilibrium mole fraction, and the activity coefcient of the IL in the saturated solution, respectively. The rst two values are given in table 2, and the experimental values are listed in table 3. The enthalpy of melting is assumed temperature independent, whereas the activity coefcient is temperature as well as solubility dependent, which can be calculated from any equation expressing excess Gibbs free energy (GE) by using the GibbsDuhem equation. In this work, one equation was used to describe the experimental results: the NRTL equation proposed by Renon and Praustnitz [31]. The molar volume of thiophene used in the equation was 219.0 cm3 g1 [32]. In the case of the solid at room temperature ILs used in this work, the molar volumes Vm,1 (T = 298.15 K) as for a hypothetical sub-cooled liquids were calculated by the group contribution method described by Barton [26]. The calculated values are listed in table 2. The applied equation has two adjustable parameters P1 and P2 (the a parameter is xed, additionally), which are determined by minimization of the objective function F(P1, P2), dened as follows:

FP 1 ; P 2

n X T exp;i T calc;i xi ; P1 ; P2 2 ; i1

where n denotes the number of experimental points. The Marquardt algorithm for solving non-linear least squares problem was successfully used in this work. As a measure of the reliability of the

TABLE 5 Correlation of the LLE data by means of the NRTL equation: parameters (g12g22 = a12T2 + b12T + c12), (g21g11 = a21T2 + b21T + c21) and deviations rx. Ionic liquid g12g22/(J mol1) a12 NRTL parametersa [B3MPy][TOS] [H3MPy][TOS] [B4MPy][NTf2] [M1,4MPy][TOS] [M2,4,6MPy][TOS] [EMIM][SCN] [BMIM][SCN] [HMIM][SCN] [Et3S][NTf2]
a

g21g11/(J mol1) b12 66.20 73.24 73.23 52.89 168.32 13.16 100.83 55.52 70.86 c12 95.54 2559 166.59 928 27944 9941 3584 4235 2519 a21 b21 81.50 47.28 85.61 72.19 155.69 55.41 423.09 142.27 163.55 c21 24755 32729 24923 26541 1447 19143 37078 6131 3345

103 rx

0.1076

0.5284

0.5 7.5 0.3 0.0 3.3 1.1 1.1 2.1 0.4

a = 0.1.

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U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311

correlations, the root-mean-square deviation of temperature, rT/K, has been calculated according to the following denition:

rT

n X T exp;i T calc;i 2 n2 i1

)1=2 : 3

The values of the parameters and the corresponding root-meansquare deviations of temperature, rT/K, are reported in table 4 and the resulting curve is presented together with the experimental points in gure 1 for ([M1,4Py][TOS] + thiophene) as an example. Unfortunately, it was impossible to correlate the SLE and the LLE results simultaneously with the same parameters. Based on values obtained, one can state that equation used was appropriate to provide a reliable description of SLE in the systems {IL (1) + thiophene (2)}. The average value of the root-mean-square deviations of temperature, rT/K, was 1.38 K. The mixtures, investigated in this work, show positive deviations from ideality in all the different solvents. The differences from ideality were not signicant in most of the systems. The values of activity coefcients in the saturated solutions ranged from 1 to about 2.3. 4.2. (Liquid + liquid) equilibrium correlation In this study, one method was used to correlate the LLE phase equilibria, based on the NRTL model. The adjustable parameters of the model (g12g22) and (g21g11) were found by minimization of the objective function OF
n X OF Dx1 2 Dx 2 ; 1 i i i1

to analogous ionic liquids in activity coefcients at innite dilution study. A comparison of phase diagrams indicate that an exchange of the anion, from tosylate to bis{(triuoromethyl)sulfonyl}imide, changes the physicochemical properties and solubility of the IL in thiophene. This is largely due to the high melting point of the tosylate-based ionic liquids; the SLE diagrams were observed versus LLE diagrams for tosylate-based ILs and [BM4Py][NTf2] ionic liquid. As a very important point for ionic liquids with the tosylate anion and with the thiocyanate anion, as well as for [Et3S][NTf2], complete miscibility was observed in the liquid phase for mixtures with thiophene up to the low mole fraction of ionic liquid (>0.14 to 0.2). Moreover, the solubility of the IL increases as the length of the carbon chain at the cation of the thiocyanate-based IL increases. It was found that the investigated ILs could be effective entrainers for separation of sulphur compounds from n-alkanes, as the solubility of thiophene in these ILs was complete over a wide range of temperature and mole fraction of the IL. The (solid + liquid) phase diagrams for the systems studied here show simple eutectic mixtures. The correlation of the SLE results was carried out by means of commonly known GE equation, viz. the NRTL. The results of the correlation of SLE and LLE were acceptable for all equations with an average RMSD of temperature rT < 1.4 K and rx < 0.007. Acknowledgments Funding for this research was provided by the Firm BASF and Dean of Faculty of Chemistry, Warsaw University of Technology, Warsaw, Poland. References
[1] A. Bsmann, L. Datsevich, A. Jess, A. Lauter, C. Schmitz, P. Wasserscheid, Chem. Commun. (2001) 24942495. [2] J. Eer, P. Wasserscheid, A. Jess, Green Chem. 6 (2004) 316322. [3] S. Zhang, Q. Zhang, Z.C. Zhang, Ind. Eng. Chem. Res. 43 (2004) 614662. [4] H. Gao, M. Luo, J. Xing, Y. Wu, Y. Li, W. Li, Q. Liu, H. Liu, Ind. Eng. Chem. Res. 47 (2008) 83848388. [5] L. Alonso, A. Arce, M. Francisco, O. Rodrguez, A. Soto, J. Chem. Eng. Data 52 (2007) 17291732. [6] L. Alonso, A. Arce, M. Francisco, A. Soto, J. Chem. Eng. Data 52 (2007) 2409 2412. [7] L. Alonso, A. Arce, M. Francisco, A. Soto, Fluid Phase Equilib. 263 (2008) 176 181. [8] L. Alonso, A. Arce, M. Francisco, A. Soto, J. Chem. Thermodyn. 40 (2008) 966 972. [9] L. Alonso, A. Arce, M. Francisco, A. Soto, J. Chem. Thermodyn. 40 (2008) 265 270. [10] L. Alonso, A. Arce, M. Francisco, A. Soto, Fluid Phase Equilib. 270 (2008) 97 102. [11] J.D. Holbrey, I. Lpez-Martin, G. Rothenberg, K.S. Seddon, G. Silvero, X. Zheng, Green Chem. 10 (2008) 8792. [12] J. Zhou, J. Mao, S. Zhang, Fuel Process. Technol. 89 (2008) 14561460. [13] P. Losada-Prez, M. Blesic, G. Prez-Snchez, C.A. Cerderia, J. Troncoso, L. Romani, J. Szydowski, L.P.N. Rebelo, Fluid Phase Equilib. 258 (2007) 715. [14] J.M. Crosthwaite, S.N.V. Aki, E.J. Maginn, J.F. Brennecke, Fluid Phase Equilib. 228229 (2005) 303309. [15] U. Domanska, K. Paduszynski, J. Phys. Chem. B 112 (2008) 1105411059. [16] U. Domanska, M. Laskowska, J. Chem. Thermodyn. 41 (2009) 645650. [17] U. Domanska, A. Marciniak, J. Phys. Chem. B 112 (2008) 1110011105. [18] U. Domanska, A. Marciniak, J. Chem. Thermodyn. 41 (2009) 754758. [19] U. Domanska, G.G. Redhi, A. Marciniak, J. Fluid Phase Equilib. 278 (2009) 97102. [20] U. Domanska, A. Marciniak, J. Chem. Thermodyn., in press, doi:10.1016/ j.jct.2009.06.011. [21] F. Mutelet, J.-N. Jaubert, M. Rogalski, J. Harmand, M. Sindt, J.-L. Mieloszynski, J. Phys. Chem. B 112 (2008) 37733785. [22] Y. Huo, S. Xia, S. Yi, P. Ma, J. Fluid Phase Equilib. 276 (2009) 4652. [23] T.M. Letcher, D. Ramjugernath, M. Krlikowski, M. Laskowska, P. Naidoo, U. Domanska, Fluid Phase Equilib. 276 (2009) 3136. [24] A.A.P. Kumar, T. Banerjee, Fluid Phase Equilib. 278 (2009) 18. [25] U. Domanska, M. Krlikowski, A. Pobudkowska, T.M. Letcher, J. Chem. Eng. Data 54 (2009) 14351441. [26] A.F.M. Barton, CRC Handbook of Solubility Parameters, CRC Press, Boca Raton, FL, 1985. [27] U. Domanska, Fluid Phase Equilib. 26 (1986) 201220.

where n is the number of experimental points and Dx is dened as

Dx xcalc xexp :

The root-mean-square deviation of mole fraction is dened as follows

rx

n n X Dx1 2 X Dx 2 i 1 i n2 n2 i1 i1

!1=2 : 6

In this calculation, the parameter a12, a constant of proportionality similar to the non-randomness constant of the NRTL equation (a12 = a21 = 0.1), was taken into account. The calculated values of the equation parameters and corresponding root-mean-square deviations are presented in table 5. All deviations are in the range rx from 0.0005 to 0.0075, being especially large for the {[H3MPy][TOS] + thiophene} binary system. For some mixtures under study, the (liquid + liquid) equilibrium values in the solvent rich phase were impossible to detect. These were detected previously for some systems of ILs with UV spectra: to within x1 % 1 104. It was assumed that the solubility in the dilute region of the ILs was in the range of a few experimental points measured in our work for [BMIM][SCN] as shown in table 3. For the other systems, it was assumed to be: x1 % 5 104 for [BM4Py] [TOS], [BM3Py][TOS] and [M1,4Py][TOS] (similar to the solubility of [BM4Py][TOS] in benzene from the UV-spectroscopic measurements [25]), x1 % 3 104 for [EMIM][SCN], [HMIM][SCN] and [Et3S][NTf2]. The results of the correlations are plotted in gures 2 and 3 for the ILs chosen. 5. Conclusions Phase equilibrium data, including SLE and LLE, for mixtures of ten pyridinium tosylate-based ionic liquids, or imidazolium thiocyanate-based ionic liquids, or sulphonium-based ionic liquid with thiophene have been measured. The results were compared

 U. Domanska et al. / J. Chem. Thermodynamics 41 (2009) 13031311 [28] U. Domanska, M. Laskowska, A. Pobudkowska, J. Phys. Chem. B 113 (2009) 63976404. [29] U. Domanska, A. Marciniak, J. Chem. Thermodyn. 40 (2008) 860866. [30] J.M. Prausnitz, R.N. Lichtenhaler, E.G. Azevedo, Molecular Thermodynamics of Fluid-Phase Equilibria, second ed., Prentice-Hall Inc., Engelwood Cliffs, New Jersey, 1986.

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[31] H. Renon, J.M. Praustnitz, AIChE J. 14 (1968) 135144. [32] B.E. Poling, J.M. Prausnitz, J.P. OConnel, The Properties of Liquid and Gases, fth ed., Mc Graw-Hill, 2001 (e-book edition).

JCT 09-165