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J. Chem. Thermodynamics 40 (2008) 640644 www.elsevier.com/locate/jct

Study on properties of ionic liquid based on ZnCl2 with 1-butyl-3-methylimidazolium chloride


Qing-Guo Zhang *, Ying Wei
College of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121013, PR China Received 29 August 2007; received in revised form 4 November 2007; accepted 6 November 2007 Available online 17 November 2007

Abstract An ionic liquid (IL) BMIZnCl3 has been synthesized by directly mixing zinc chloride (ZnCl2) and 1-butyl-3-methylimidazolium chloride (BMIC) with molar ratio 1/1 under a dry argon atmosphere. The density and surface tension of the IL in temperature range from 313.2 K to 343.2 K were determined. The value of thermal expansion coecient and surface entropy were estimated by extrapolation. In terms of Glassers theory, the standard molar entropy and lattice energy of the IL were estimated. Using the methods of Kabo and Rebelo, the molar enthalpy of vaporization of the IL, Dg H  at T = 298 K and Dg H  at the hypothetical normal boiling point were estimated. l l m m The thermal expansion coecient, a, calculated by the interstice model is of the same order of magnitude as the experimental value. 2007 Elsevier Ltd. All rights reserved.
Keywords: Ionic liquid; Density; Surface tension; Interstice model; Enthalpy of vaporization

1. Introduction An ionic liquid (IL) is an ionic compound, which exhibits ionic conductivity, and it is a liquid below T = 373 K [1]. Because of the great potential as green solvents, ionic liquids (ILs) have been attracting great interest in the last decade and have received extensive attention from the academic and industrial communities [15]. Though the ILs based on AlCl3 have been most widely studied, they were infrequently used as solvent systems due to their sensitivity to moisture and air [6,7]. Recently, it is found that the ILs based on ZnCl2 constitute a new type of ionic liquid, air- and moisture-stable, friendly to the environment and with catalytic activity in many reactions [4,810]. In addition, it can be very useful for the electro-deposition of pure metals and alloys [11,12] and in other specialized elds [1315]. As a continuation of our previous investigations of ionic liquids [1618], this paper reports the synthesis of the ionic liquid BMIZnCl3 by directly mixing ZnCl2 and 1-butyl-3-methyl-

imidazolium chloride (BMIC) with a molar ratio 1/1 under a dry argon atmosphere. In this paper, we adopted Lecocqs viewpoint [19] viz.: IL compounds with molar ratio BMIC/ ZnCl2 = 1/1 is BMIZnCl3. The density and surface tension of BMIZnCl3 were determined over the temperature range of 313.2 K to 343.2 K. The value of the thermal expansion coecient and surface entropy were estimated by extrapolation. In terms of Glassers theory, the standard molar entropy and crystal energy of BMIZnCl3 were estimated [20]. Using the methods of Kabo [21] and Rebelo [22], the molar enthalpy of vaporization of the IL, Dg H  at l m T = 298 K and Dg H  at the hypothetical normal boiling l m point were obtained. In order to compare with experimental values, the thermal expansion coecient was calculated by the interstice model [23], and their magnitude is of the same order. 2. Experimental 2.1. Chemicals

Corresponding author. Fax: +86 416 3400292. E-mail address: zhangqguo23@yahoo.com.cn (Q.-G. Zhang).

The 1-methylimidazole (AR grade reagent), obtained from ACROS, and chlorobutane of AR grade reagent,

0021-9614/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.jct.2007.11.003

Q.-G. Zhang, Y. Wei / J. Chem. Thermodynamics 40 (2008) 640644

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obtained from Beijing Chemicals Co., were distilled under a nitrogen atmosphere before use. Ethyl acetate and acetonitrile were distilled and then stored over molecular sieves in tightly sealed glass bottles. Anhydrous ZnCl2 (mass fraction purity 0.9999) was purchased from Aldrich, opened in the glove box lled with dry argon, and used without further purication. 2.2. Preparation of BMIC/ZnCl2 ionic liquids The BMIC (1-butyl-3-methylimidazolium chloride) was synthesized by Wilkes method [24]. The melting point of the product is T = (339 to 341) K. Its n.m.r. spectrum is in good agreement with that in the literature. The ZnCl2 was added slowly with stirring to a small glass vial containing BMIC (molar ratio of BMIC/ZnCl2 = 1/1) in a glovebox lled with dry argon, then heated to T = 363 K for 48 h. The colourless and transparent ionic liquid compound, BMIZnCl3, was obtained. 2.3. Measurement of density and surface tension First, the densities of water were measured by Westphal balance and were in good agreement with those in the literature [25] within experimental error 0.0001 g cm3 at T = 313.2 K to (343.2 0.1) K. Then the density of BMIZnCl3 was measured by the same method under dry argon at the same temperatures. After the surface tension of water was measured by the forced bubble method, the results were in good agreement with that in the literature [25] within experimental error 0.1 mJ m2 at T = 313.2 K to T = (343.2 0.1) K. The values of surface tension of BMIZnCl3 were measured by the same method under dry argon at the same temperatures. 3. Results and discussion 3.1. Density and surface tension measurements The values of density, q, and surface tension, c, of BMIZnCl3 are listed in table 1. Each value in table 1 is the average of three determinations. The experimental values of ln q against T were tted by the method of least-squares and empirical equations ln q = 0.5271 to 5.36 104 (T/K) was obtained. See gure 1. The correlation coecient, r =
TABLE 1 The values of surface tension, c, and density, q, of the ionic liquid BMIZnCl3 T/K 313.2 318.2 323.2 328.2 333.2 338.2 343.2 q/(g cm3) 1.4319 1.4281 1.4248 1.4207 1.4165 1.4128 1.4093 c/(mJ m2) 57.49 56.90 56.62 56.16 55.70 55.40 54.79

0.368 0.36 0.352 0.344 0.336 310

320

330 T/K

340

350

FIGURE 1. Plot of ln q against temperature for IL BMIZnCl3: (j) experimental values; line, linear t.

0.999, and standard deviation, s = 1.8 104, of the linear t were obtained. The slope of the tting equation is the thermal expansion coecient of BMIZnCl3 at T = 298.2 K, a, as it is dened by the following equation: a o ln q=oT p : 1

The value of a (exp) obtained from the slope of the linear t was 5.36 104 K1. 3.2. Estimation of the crystal energy and standard entropy of BMIZnCl3 From the experimental values of density, the molar volume, Vm, of BMIZnCl3 was calculated using the following equation: V m M=N q; 2 where M is average molar mass and N is Avogadros constant. The value of q at T = 298.2 K, 1.4322 g cm3, was obtained by extrapolation of the experimental data. The calculated value of Vm for BMIZnCl3 is 0.3545 nm3. According to the previous work [26], the volume of the cation is 0.2751 nm3, so that the volume of the anion is 0.0794 nm3. Compared with the previous study of IL based on aluminium [27], it is found that the Vm of BMIZnCl3 is less than the Vm of the BMIAlCl4, 0.4133 nm3, because of the smaller volume of the anion ZnCl . 3 In terms of Glassers theory [20], the standard molar entropy, S0/J K1 mol1, and the crystal energy, UPOT/ kJ mol1 of the IL can be estimated by the following equations: S 0 =J K1 mol1 1246:5V m =nm3 per formula 29:5; 3 and U POT =kJ mol1 234:6=V 1=3 103:8: m 4

The value of the standard molar entropy of BMIZnCl3 calculated by equation (3), S0(298.2 K)/J K1 mol1, is 471.4 and the crystal energy of BMIZnCl3 calculated by equation. (4), Upot(298.2 K)/kJ mol1, is 435.3. The calculated value of the crystal energy of BMIZnCl3 is very close

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Q.-G. Zhang, Y. Wei / J. Chem. Thermodynamics 40 (2008) 640644

to that of the ILs based on ferric [26]. In comparison with fused salts, the crystal energy of BMIZnCl3 is much lower, for example, UPOT = 613 kJ mol1 for fused CsI at T = 298.2 K [25], which has the smallest crystal energy among alkali halides. The low crystal energy is the underlying reason for the formation of the ionic liquid at room temperature. 3.3. Estimation of the surface properties for the ionic liquid BMIZCl3 In general, surface tension, c, of many liquids decreases almost linearly while temperature increases and the relationship is expressed by the Eotvos equation [28]: cV 2=3 kT C T ; 5

58 57
/(mJm )
-2

56 55 54 310

320

330 T/K

340

350

FIGURE 3. Plot of surface tension c against temperature for IL BMIZnCl3: (j) experimental values; line, linear t.

3.4. Estimation of the vaporization enthalpies of the BMIZCl3 Kabo et al. [21] put forward an empirical equation for estimation of the enthalpy of vaporization, Dg H  (298 K), l m of ionic liquids: Dg H  298 K AcV 2=3 N 1=3 B; l m 6

where V is the molar volume of the liquid, TC is critical temperature, and k is an empirical constant. The linear regression of the plot of cV2/3 against T obtained from this experiment (see gure 2), produced the values of k and TC as 2.51 107 J K1 and 1240 K, respectively. In general, the value of k is interrelated with the polarity of liquid. For a majority of organic liquids, k is about 2.1 107 J K1 but for fused salts with larger polarity, it is rather small [28]. For example, k = 0.4 107 J K1 for fused NaCl. Therefore, the magnitude of k can represent the polarity of ionic liquid. As may be seen from the value of k for BMIZnCl3, this implies that the polarity of BMIZnCl3 is close to that of an organic liquid. The surface tension of BMIZnCl3 obtained at dierent temperatures had been regressed against T by the leastsquares, and a straight line was obtained (see gure 3) and the correlation coecient is 0.99. From the slope (oc/ oT)p, the surface excess entropy at T = 298.2 K, Sa = (oc/oT)p = 89.23 106 J m2, was obtained. The surface excess energy at T = 298.2 K, Ea, likewise was obtained by equation: Ea = c T(oc/oT)p = 85.46 J m2. By comparison with fused salts, for example, Ea = 146 mJ m2 for fused NaNO3 and the value of Ea for BMIZnCl3 is much lower, but is larger than that of the organic liquid, for example, 67 mJ m2 for benzene and 51.1 mJ m2 for n-octane [28].

0.210 0.207

2/3

0.204 0.201 0.198 310

where N is Avogadros constant, A and B are empirical parameters with values A = 0.01121 and B = 2.4 kJ mol1. The molar enthalpy of vaporization for IL compound BMIZnCl3 was calculated from equation. (6) and the result was 285.2 kJ mol1. Rebelo et al. [22] put forward a method for estimating the hypothetical temperature of the normal boiling point (TNBP) of the ionic liquid, Tb, in terms of critical temperature, Tc, obtained from Eotvos equation. The relationship between Tb and Tc can be described as Tb % 0.6 Tc for IL based on the fact that this relation stands for most of the substances [22], so Tb of the BMIZnCl3 was 745 K. Using the aforementioned normal boiling point of BMIZnCl3 and a Troutons constant (%90 J mol1 K1), the molar enthalpy of vaporization at TNBP for this ionic liquid was estimated to be 67.0 kJ mol1. The dierence between Dg H  (Tb) estimated by Rebelos method and Dg H  l l m m (298 K) estimated by Kabos method is caused by the heat capacity dierence between the liquid and the gas phases at dierent temperatures. Supposing linear change of Dg H  with temperature in the temperature range between l m 298 K and Tb, the vapour pressure, p, of the IL may be estimated by the ClapeyronClausius equation. The estimated value of p at T = 298 K was 7.1 1018 Pa for BMIZnCl3. The value of p at T = 298 K is very small and the result is in good agreement with our experience: ionic liquids have a negligible vapour pressure at ambient temperature [22,29]. 3.5. Estimation of the thermal expansion coecient by the interstice model

/(10 J)

320

330 T/K

340

350

FIGURE 2. Plot of cV2/3 against temperature for IL BMIZnCl3: (j) experimental values; line, linear t.

If the hole model of molten salts [30] were transplanted to pure ionic liquid, a new theoretical model results, which is called the interstice model [23,31]. The model was built on the basis of the following assumptions: (1) Given the

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large size and the asymmetric shape, the ions may not be closely packed and many interstices between ions come into existence; (2) In order to calculate the volume easily, the interstice is regarded as a bubble; (3) There are 2N interstices for 1 mole 11 ionic liquid, where N is Avogadros constant [4]. The interstice in ILs can move about like an ion or another particle. During this process, the interstice does not vanish, but can be compressed and expanded, which has an extra feature of motion of an interstice called the breathing motion. Following the same procedure using the hole model of the molten salt together with previous work [31], the expression for the calculation of interstice volume, v, is obtained by the classical statistical mechanics: v 0:6791fk B T =cg
3=2

where kB is Boltzmanns constant, T thermodynamic temperature, c surface tension of the ionic liquid. From equation. (7), the value of the average volume of the interstices of the ionic liquid BMIZnCl3 can be obtained. From table 1, the surface tension of BMIZnCl3 at T = 298.2 K was obtained by extrapolation, and the average volume of interstice, v = 12.55 1024 cm3, was calculated and listed in table 2. The molar volume of the ionic liquid, V consists of the inherent volume, Vi, and total volume of the all interstices, P v 2Nv, that is V V i 2Nv: 8 If the expansion of the IL volume only results from the expansion of the interstices when temperature increases, then expression for a is derived from the interstice model: a 1=V oV =oT p 3Nv=VT : 9

of fused salts [30]. In fact, there is a great dierence between the interstice model and the hole model. The hole model is designed to describe spontaneous density uctuations of molecular extent that occur in liquids, as the constituent particles move about under thermal agitation. In the solid crystal, one important such density uctuation that appears in equilibrium at high temperatures is the unoccupied lattice site, or missing particle. On account of the rigid geometrical structure of the crystal, such a small low-density region can be equal in size to only one characteristic elementary volume, determined by the crystal structure. Furthermore, motion of these empty regions can proceed only by discrete jumps, produced by a shift of a particle in the crystal into a neighbouring unoccupied site. However, the situation in the liquid is much less restrictive, since extra freedom of particle movement attending the melting of the rigid crystal implies not only a continuum of possible sizes and shapes for the low-density regions, or holes, but movement of these holes may occur by a relatively continuous drift, rather than by discrete jumps. However, in the interstice model, the inherent interstices exist in the ionic liquid on account of the large size and great asymmetry of ions and they cannot vanish during thermal movement. This is conrmed by other experimental results that are listed in table 2. Acknowledgements This project was supported by NSFC (20473036) and Bureau of Liaoning Province (2004066C) PR China. References
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The values of a for BMIZnCl3 calculated by equation (9), a (cal), are listed in table 2 and compared to the experimental values a (exp). The comparison shows that both values are of the same order of magnitude, which implies that the interstice model is reasonable. It is noted that there are probably certain semantic confusions in the name of this model with that of hole model
TABLE 2 The values of parameters for the interstice model at T = 298.2 K Ionic liquid BMIZnCl3 BMIAlCl4 BMIGaCl4 BMIInCl4 BMIFeCl4 EMIInCl4 EMIFeCl4 EMISE BMIBF4 Vm/nm3 0.3545 0.4130 0.4109 0.4225 0.4097 0.3725 0.3525 0.3190 0.3105 1024v/cm3Calc 12.55 18.40 18.70 19.50 18.16 14.86 20.51 16.54 19.19 3.53 6.21 4.58 4.64 4.46 4.01 5.85 5.24 6.22 104a/K1Exp 5.36 4.48 5.98 6.50 4.74 6.53 5.96 5.37 5.68 This work a b c [31] [17] [26] [23] d

Taken from (a) J. Tong et al., Acta Phis-Chim. Sin. 21 (2006) 71. (b) Taken from W.-G. Xu et al., Chin. J. Chem. 24 (2006) 331. (c) Taken from J.-Z. Yang, Q.-G. Zhang, et al., Chem. J. Chin. Univ., 26 (2006) 10. (d) Taken from J.-Z. Yang, J.-S. Gui, X.-M. Lu, Q.-G. Zhang, H.-W. Li, Acta Chim. Sin., 63 (2005) 577580.

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JCT 07-259

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