J. Chem.

Thermodynamics 60 (2013) 914

Contents lists available at SciVerse ScienceDirect

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

Application of 1-alkyl-3-methylpyridinium bis(triuoromethylsulfonyl)imide ionic liquids for the ethanol removal from its mixtures with alkanes
Begoa Gonzlez , Sandra Corder, Alberto G. Santamara
Advanced Separation Processes Group, Department of Chemical Engineering, University of Vigo, Campus Lagoas-Marcosende, 36310 Vigo, Spain

a r t i c l e

i n f o

a b s t r a c t
In this work, two ionic liquids 1-ethyl-3-methylpyridinium bis(triuoromethylsulfonyl)imide, [EMpy][NTf2], and 1-methyl-3-propylpyridinium bis(triuoromethylsulfonyl)imide, [PMpy][NTf2], were investigated as possible solvents in the extraction processes for the ethanol removal from its mixtures with heptane and hexane. Hence, the experimental determination of the (liquid + liquid) equilibrium (LLE) for the ternary systems {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)} and {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)} at T = 298.15 K and atmospheric pressure was carried out. The solute distribution ratio and selectivity were calculated to evaluate the capability of these ionic liquids for the extraction of ethanol. Moreover, comparisons with other ILs taken from the literature were made. Finally, the experimental LLE values were compared with the correlated values obtained by means of the NRTL thermodynamic model. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 21 November 2012 Accepted 18 December 2012 Available online 7 January 2013 Keywords: Ionic liquids (Liquid + liquid) equilibrium Ethanol Azeotropic mixtures Extraction

1. Introduction The scientic community has focused their research on green processes because of the growing health and environmental awareness. Ionic liquids (ILs) are gaining wide recognition as potential environmental solvents employed to separate liquid mixtures, mainly due to their negligible vapour pressure [1], which leads to negligible solvent emissions. Furthermore, ILs show other interesting properties such as chemical stability at high temperatures, wide liquid range, simple regeneration and high solubility for both polar and non-polar organic and inorganic compounds [2]. Moreover, ILs are known as designer solvents, due to the possibility of tuning their cation or anion to achieve specic properties for a specic task. For many years, lead derivatives were used as additives for gasoline to enhance the octane index. Nowadays, oxygenated compounds are used as a safe alternative to the conventional lead addition. However, solvent mixtures containing azeotropes such as heptane or hexane with ethanol are present in the process of manufacturing. The separation of these mixtures into pure components is necessary in order so they can be reused, but by means a simple distillation becomes impossible. The extractive distillation is often used to remove one of the components in the azeotropic system. Nevertheless, high energy cost to achieve a uid phase system, volatile compounds, or high pressures are serious disadvantages. The liquid + liquid extraction, based on the immiscibility of two liquid phases, has come out as an alternative benecial separation process to extractive distillation [3].
Corresponding author. Tel.: +34 986812292.
E-mail address: bgp@uvigo.es (B. Gonzlez). 0021-9614/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jct.2012.12.017

Recently, a few works concerning separation of azeotropic mixtures alkane/alcohol involving ILs as extracting agents have been published [310], consequently, new investigations, in which other ionic liquids are studied, result necessary. As a continuation of our recent investigations of azeotropic separations [1113], the ionic liquids 1-ethyl-3-methylpyridinium bis(triuoromethylsulfonyl)imide, [EMpy][NTf2], and 1-methyl-3-propylpyridinium bis(triuoromethylsulfonyl)imide, [PMpy][NTf2], were considered to be tested as extracting solvents for the ethanol separation from its azeotropic mixtures with heptane and hexane. In this way, the effect of the alkyl chain length of the pyridinium cation on the extraction process can be evaluated. Besides, these ILs with [NTf2]- anion were selected due to their relatively low viscosity as well as their easy availability [14]. In order to understand the role of ionic liquids in separation process, (liquid + liquid) equilibrium (LLE) data are required. Therefore, the LLE for the ternary systems {heptane or hexane (1) + ethanol (2) + [EMpy][NTf2] or [PMpy][NTf2] (3)} at T = 298.15 K and atmospheric pressure has been investigated. Likewise, the solute distribution ratio and the selectivity were calculated to evaluate the capacity of the chosen ILs as azeotrope breakers. Finally, the experimental LLE values were correlated by the Non Random Two Liquid (NRTL) thermodynamic model [15].

2. Experimental 2.1. Chemicals The chemicals were supplied by SigmaAldrich for heptane and hexane, and by Merck for ethanol. The ILs [EMpy][NTf2] and

10

B. Gonzlez et al. / J. Chem. Thermodynamics 60 (2013) 914

[PMpy][NTf2] studied were purchased from IoLiTec, and their structures are shown in gure 1. To reduce the water content and volatile compounds to negligible values, vacuum (P = 0.2 Pa) and moderate temperature (T = 343 K) were applied to the ILs during at least 48 h. Therefore, the water content values after the drying step were slightly lower but in the same order that those supplied by the company. All chemicals were kept in bottles inside a glove box under argon atmosphere, where they were always manipulated. The purities, water content by mass, ww, and concentration of halides, whalide, supplied by the companies are listed in table 1. Moreover, in order to assess their validity, densities and refractive indices of the pure components were measured at T = 298.15 K, and these data are also shown in table 1, together with the available literature values [5,16,17]. 2.2. Apparatus Densities of pure components and their mixtures were measured using an Anton Paar DSA-5000 M digital vibrating-tube densimeter with an uncertainty in the experimental measurements of 3 x 105 gcm3. Refractive indices were determined by an automatic refractometer Abbemat-HP Dr. Kernchen with an uncertainty in the experimental measurements of 4 x 105. Moreover, all samples were prepared by weight just before their use, using a Mettler AX-205 Delta Range balance with an uncertainty of 3 x 104 g. 2.3. Experimental LLE procedure Experimental LLE tie-lines determination was performed into glass cells containing a magnetic stirrer with silicon covers and thermostatically controlled at T = 298.15 K. Immiscible ternary mixtures of known composition were placed into the cells, immediately, each mixture was stirred vigorously for 6 h in order to allow the correct contact between phases. Then, cells were placed overnight in a thermostatic bath (PoliScience digital temperature controller, with a digital thermometer ASL model F200 with an uncertainty of 0.01 K) to ensure a complete split of the equilibrium phases. Next, samples of both equilibrium phases were withdrawn with a syringe and their densities were determined. Finally,

TABLE 2 Experimental LLE data on mole fraction, solute distribution ratio, b, and selectivity, S, for the ternary systems studied at T = 298.15 K and po = 101.3 kPa. Upper phase xI 1 1.000 0.981 0.958 0.887 0.754 0.616 0.518 0.444 0.371 1.000 0.989 0.971 0.927 0.715 0.586 0.474 0.423 1.000 0.983 0.964 0.920 0.875 0.752 0.667 0.569 1.000 0.991 0.973 0.925 0.804 0.649 0.566 0.447 0.369 xI 2 Lower phase xII 1 xII 2 (3)} 8.04 7.46 4.21 2.40 1.67 1.40 1.24 1.13 213.18 191.32 87.89 38.99 20.33 13.29 9.72 7.01 b S

{Heptane (1) + Ethanol (2) + [EMpy][NTf2] 0.000 0.042 0.000 0.019 0.037 0.153 0.042 0.037 0.311 0.113 0.042 0.475 0.246 0.046 0.590 0.384 0.051 0.641 0.481 0.054 0.672 0.554 0.057 0.688 0.626 0.060 0.707

{Hexane (1) + Ethanol (2) + [EMpy][NTf2] (3)} 0.000 0.067 0.000 0.011 0.057 0.163 14.60 0.029 0.058 0.309 10.84 0.073 0.060 0.470 6.41 0.285 0.068 0.571 2.00 0.413 0.072 0.618 1.50 0.524 0.074 0.639 1.22 0.573 0.075 0.666 1.16 {Heptane (1) + Ethanol (2) + [PMpy][NTf2] 0.000 0.058 0.000 0.017 0.056 0.126 0.036 0.052 0.306 0.080 0.053 0.444 0.125 0.055 0.519 0.247 0.064 0.635 0.332 0.066 0.670 0.429 0.069 0.701 (3)} 7.40 8.43 5.54 4.14 2.57 2.02 1.63

254.61 182.15 98.91 21.10 12.09 7.82 6.53

130.09 155.09 96.10 66.04 30.43 20.41 13.39

{Hexane (1) + Ethanol (2) + [PMpy][NTf2] (3)} 0.000 0.094 0.000 0.009 0.088 0.121 13.47 0.027 0.082 0.299 11.23 0.075 0.080 0.432 5.76 0.196 0.081 0.563 2.88 0.350 0.090 0.634 1.81 0.433 0.094 0.658 1.52 0.550 0.101 0.689 1.25 0.624 0.108 0.711 1.14

152.32 133.58 66.42 28.76 13.04 9.15 5.57 3.89

Standard uncertainties u are u(x) = 0.007 and u(T) = 0.01 K.

(a)
N (CF3SO2)2N

(b)
N (CF3SO2)2N

FIGURE 1. Structures of the ionic liquids studied in this work: (a) [EMpy][NTf2] and (b) [PMpy][NTf2].

their compositions were inferred using the solubility curves, which were previously constructed by the cloud point method at 298.15 K, i.e. binary mixtures of known composition were titrated with the third component until turbidity in the samples was observed [18]. Then, the samples were weighed and the densities measured. This way, a polynomial expression (density versus mole fraction) can be obtained. Three validation points were evaluated to estimate the error of the technique used for the determination of the solubility curves. The uncertainty of the phase composition was estimated to be 0.007 in mole fraction.

TABLE 1 Purity, water content by mass, ww, concentration of halides, whalide, density, q, and refractive index, nD, of pure components at T = 298.15 K and po = 101.3 kPa. Component Mass fraction purity ww (106) whalide (106)

q/(gcm3)
Exp. Lit. n.a. 1.4475a 0.67946b 0.65484b 0.7851c 1.48850 1.44794 0.67957 0.65520 0.78520

nD Exp. 1.44376 1.44485 1.38529 1.37241 1.35936 Lit. n.a. n.a. 1.38511b 1.37226b 1.35929c

[EMpy][NTf2] [PMpy][NTf2] Heptane Hexane Ethanol

>0.99 >0.99 >0.99 >0.99 >0.99

80 90 n.a. n.a. n.a.

<100 <100 n.a. n.a. n.a.

Standard uncertainties u are u(q) = 0.00003 gcm3, u(nD) = 0.00004 and u(T) = 0.01 K. n.a.: not available. a Reference [16]. b Reference [17]. c Reference [5].

B. Gonzlez et al. / J. Chem. Thermodynamics 60 (2013) 914

11

(a)
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4

Ethanol
0.0 0.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.5 0.6 0.7 0.8 0.9 1.0 0.0

(b)
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3

Ethanol
0.0 0.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0

Heptane

[EMpy][NTf2] Ethanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

Hexane

[EMpy][NTf2] Ethanol
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

(c)

(d)

0.8 0.9 1.0

0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Heptane

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.0

1.0

0.0

[PMpy][NTf2]

Hexane

[PMpy][NTf2]

FIGURE 2. Experimental and calculated LLE results for the ternary systems: (a) {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}; (b) {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}; (c) {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)} and (d) {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)} at T = 298.15 K. Solid circles and solid lines represent experimental tie-lines, and open squares and dashed lines represent calculated data using the NRTL model.

3. Results and discussion 3.1. (Liquid + liquid) equilibrium data The measured compositions of the experimental tie-line ends for the four ternary systems studied {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)} and {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)} at T = 298.15 and atmospheric pressure are reported in table 2. The corresponding triangular diagrams containing the experimental LLE values are presented in gure 2, where a visualization of the slopes of the tie-lines as well as the shape of the immiscibility region is shown. As it can be seen in that gure, an increase in the size of the alkyl chain length of the studied ILs leads to a decrease of the immiscibility region. Besides, heptane shows a lower solubility than hexane in the tested ILs. On the other hand, the positive slopes of the tie lines indicate that the ethanol has a more afnity toward the investigated ILs than toward the heptane or hexane. The solute distribution ratio, b, and selectivity, S, were calculated to evaluate the extraction capacity of the ILs according to the equations:
I b xII 2 =x2 ;

I I II S xII 2 x1 =x2 x1 ;

where x is the molar composition, superscripts I and II indicate the upper phase and lower phase, respectively, and subscripts 1 and 2 refer to the heptane or hexane and ethanol, respectively. High values of these parameters are necessary to consider an IL a good candidate for an extraction process. Values of b and S for each experimental tie-line are reported in table 2. The behaviour of the solute distribution ratio and selectivity for each system as a function of the ethanol mole fraction in the upper phase can be observed in gures 3 and 4, respectively. Besides, comparisons with literature data for the ternary systems {heptane (1) + ethanol (2) + [EMim][NTf2] (3)} [12], {heptane (1) + ethanol (2) + [PMim][NTf2] (3)} [12], {hexane (1) + ethanol (2) + [EMim] [NTf2] (3)} [11], {hexane (1) + ethanol (2) + [BMpy][NTf2] (3)} [11], and {hexane (1) + ethanol (2) + [PMim][NTf2] (3)} [13] were also made. As can be observed from these gures, b and S decrease with the content of ethanol in the upper phase. As illustrated in gure 3(a) and (b), for all of the assayed systems, the b values are not inuenced signicantly by the alkyl chain length of the cation, being of the same order of magnitude for the [EMpy][NTf2] and [PMpy][NTf2] in the systems with heptane and also in the systems with hexane. When the values for the ionic liquid [BMpy][NTf2], which were taken from the literature

12

B. Gonzlez et al. / J. Chem. Thermodynamics 60 (2013) 914

(a)

20

(a)
500

Solute distribution ratio ()

15

400

Selectivity (S)
0.2 0.4 0.6

300

10

200

5
100

0 0.0

0 0.0

0.2

0.4

0.6

x2

x2

(b)
40

(b)
800

Solute distribution ratio ()

30

600

20

Selectivity (S)
0.2 0.4 0.6

400

10

200

0 0.0

x2

0 0.0

0.2

0.4

0.6

x2 I
FIGURE 4. Selectivity for the ternary systems with heptane (a) and hexane (b) at T = 298.15 K: (N) {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}; () {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)}; (d) {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}; (j) {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)}; (e) {heptane (1) + ethanol (2) + [EMim][NTf2] (3)} from reference [12]; (+) {heptane (1) + ethanol (2) + [PMim][NTf2] (3)} from reference [12]; (s) {hexane (1) + ethanol (2) + [EMim][NTf2] (3)} from reference [11]; (4) {hexane (1) + ethanol (2) + [PMim][NTf2] (3)} from reference [13]; and () {hexane (1) + ethanol (2) + [BMpy][NTf2] (3)} from reference [11].

FIGURE 3. Solute distribution ratio for the ternary systems with heptane (a) and hexane (b) at T = 298.15 K: (N) {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}; () {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)}; (d) {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}; (j) {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)}; (}) {heptane (1) + ethanol (2) + [EMim][NTf2] (3)} from reference [12]; ( + ) {heptane (1) + ethanol (2) + [PMim][NTf2] (3)} from reference [12]; (s) {hexane (1) + ethanol (2) + [EMim][NTf2] (3)} from reference [11]; (4) {hexane (1) + ethanol (2) + [PMim][NTf2] (3)} from reference [13]; and () {hexane (1) + ethanol (2) + [BMpy][NTf2] (3)} from reference [11].

[11], are compared with the [EMpy][NTf2] and [PMpy][NTf2] in the systems with hexane, slightly higher values of b for the [BMpy][NTf2] can be seen. Moreover, comparing the ternary systems tested with the same IL and different alkane, it is possible to observe that the ILs in the systems with hexane show higher values of b at low concentrations of ethanol than the ILs in the systems with heptane. The same results were achieved when the ternary systems taken from literature {heptane (1) + ethanol (2) + [EMim][NTf2] or [PMim][NTf2] (3)} [12] and {hexane (1) + ethanol (2) + [EMim][NTf2] or [PMim][NTf2] (3)} [11,13] were

compared. Furthermore, the effect of the cation of the ionic liquid was analysed comparing the experimental and literature data for the following pairs of pyridinium- and imidazolium-based ILs: [EMpy][NTf2] / [EMim][NTf2] and [PMpy][NTf2] / [PMim][NTf2] as in the systems with heptane as in the systems with hexane. The b values for the imidazolium- and pyridinium-based ILs are similar when the concentrations of ethanol are increased, but at low mole fractions of ethanol, the imidazolium-based ILs present higher values of b than the pyridinium-based ILs.

B. Gonzlez et al. / J. Chem. Thermodynamics 60 (2013) 914 TABLE 3 Values of the NRTL parameters and root-mean-square deviation of the composition, rx, obtained from LLE data correlation at T = 298.15 K. ij 12 13 23 12 13 23 12 13 23 12 13 23

13

Dgij/(kJmol1)

Dgji/(kJmol1)

aij

rx
0.319

of the NRTL model are also given in table 3 together with the root-mean-square deviation of the composition, rx. This deviation, which provides a measure of the precision of the correlations, is calculated according to the following expression:

{Heptane (1) + Ethanol (2) + [EMpy][NTf2] (3)} 6.04 0.80 0.20 12.52 5.07 0.20 1025.62 0.51 0.30 {Hexane (1) + Ethanol (2) + [EMpy][NTf2] (3)} 6.09 1.75 0.12 26.71 0.13 0.12 22.62 11.68 0.12 {Heptane (1) + Ethanol (2) + [PMpy[NTf2] (3)} 13.64 1.99 0.30 19.46 0.66 0.14 4.90 21.01 0.25 {Hexane (1) + Ethanol (2) + [PMpy][NTf2] (3)} 3.80 0.86 0.18 24.19 2.21 0.18 17.19 8.20 0.18

P P h M N 1

rx 100

;calc 2 II;calc 2 xIij xI xII 1j xij ij

i1=2 ; 4

2MN

0.197

0.585

where M is the number of tie-lines and N is the number of components in the mixture. The low values for the root-mean-square deviations indicate that good correlations of the experimental values with the NRTL model were obtained. In addition, a good coincidence between the experimental and calculated values was observed in the triangular diagrams of gure 2. 4. Conclusions

0.153

With respect to the selectivity values (gure 4(a) and (b)), these were higher than one for the assayed ILs in the systems with heptane as well as in the systems with hexane. As a result, these ILs could be used as extraction solvents for the separation of ethanol from heptane and hexane. As it can be inferred from gure 4, the increase of the alkyl chain length in the pyridinium ring of the ILs leads to a decrease of selectivity as in the systems with heptane as in the systems with hexane. Moreover, comparing the systems with heptane with those systems with hexane, the selectivity values increase in the order: heptane > hexane, which is in concordance with the increasing size of the immiscibility region. Just as the solute distribution ratio values, selectivity values were higher for the imidazolium-based ILs taken from literature at low mole fractions of ethanol than for the tested pyridinium-based ILs, and selectivity values were similar when the concentration of ethanol was increased for both imidazolium- and pyridinium-based ILs. Taking everything into consideration, the ionic liquid [EMpy][NTf2] can be considered to be the best candidate of the studied ILs to act as solvent for ethanol extraction from its azeotropic mixtures with heptane and hexane. Besides, regarding the size of the alkanes involved in each system, a purer ethanol can be obtained in the systems with heptane than in the systems with hexane. 3.2. Data correlation A thermodynamic model such as the Non Random Two Liquid, NRTL [15], was used to correlate the experimental LLE data for the four ternary systems studied. In spite of the fact that NRTL was initially developed for non-electrolyte solutions, previous references conrm that this model is able to correlate satisfactorily LLE data of systems involving ILs [8,9,11,12,19]. The non-randomness parameter, a, was subject to optimization between 0.05 and 0.3 during calculations, and the best results achieved are those reported in table 3. The next objective function was used to minimize the difference between the experimental and calculated mole fractions:

(Liquid + liquid) equilibrium data for four ternary systems {heptane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {hexane (1) + ethanol (2) + [EMpy][NTf2] (3)}, {heptane (1) + ethanol (2) + [PMpy][NTf2] (3)} and {hexane (1) + ethanol (2) + [PMpy][NTf2] (3)} were determined at T = 298.15 K and atmospheric pressure. The solute distribution ratio and selectivity values were calculated and compared with other values reported in the literature. The values of S and b for the tested ILs were greater, especially at low mole fractions of ethanol. As a result, these ILs could be considered as suitable solvents for the extraction of ethanol from heptane and hexane and small quantity of these ionic liquids would be required for the extraction process. Moreover, the increasing of the alkyl chain length of the pyridinium ring leads to similar values of the solute distribution ratio and a decrease of selectivity. Regarding the size of the alkane, it can be observed slightly lower values of b at low mole fractions of ethanol and higher values of S over the whole range of composition for the systems with heptane than for the systems with hexane. Therefore, the ionic liquid [EMpy][NTf2] can be considered the best candidate for the separation of ethanol from its mixtures with heptane and hexane, and being obtained a more efcient extraction process when heptane is involved. With regard to the imidazolium-based ILs taken from the literature ([EMim][NTf2] and [PMim][NTf2]), these yielded higher values of b and S than the investigated pyridiniumbased ILs when the concentration of ethanol was diminished. Finally, the NRTL model was found to correlate appropriately the experimental LLE data for the four studied ternary systems. Acknowledgments S. Corder is thankful to Xunta de Galicia for her predoctoral grant (Plan I2C). B. Gonzlez is grateful to Comisin Interministerial de Ciencia y Tecnologa for nancial support via the Ramn y Cajal Programme (RYC-2008-02388). The authors are also grateful to the Xunta de Galicia for nancial support through the project 10PXIB314124PR. References
[1] M.J. Earle, J.M.M.S. Esperana, M.A. Gilea, J.N. Canongia Lopes, L.P.N. Rebelo, J.W. Magee, K.R. Seddon, J.A. Widegren, Nature 439 (2006) 831834. [2] K.R. Seddon, J. Chem. Technol. Biotechnol. 68 (1997) 351356. [3] U. Domanska, Z. Zoek-Tryznowska, A. Pobudkowska, J. Chem. Eng. Data 54 (2009) 972976. [4] T.M. Letcher, N. Deenadayalu, B. Soko, D. Ramjugernath, J. Chem. Eng. Data 48 (2003) 904907. [5] A.B. Pereiro, A. Rodrguez, Fluid Phase Equilibr. 270 (2008) 2329. [6] A.B. Pereiro, A. Rodrguez, Sep. Pur. Technol. 62 (2008) 733738. [7] A.B. Pereiro, A. Rodriguez, Chem. Eng. J. 153 (2009) 8085. [8] A.B. Pereiro, F.J. Deive, M.S.S. Esperana, A. Rodrguez, Fluid Phase Equilibr. 291 (2010) 1317.

O:F:

M h X i1

;calc 2 I;calc 2 xI1i xI xI 2 i x2 i li

M h X i1

i II;calc 2 II;calc 2 xII xII ; 1 i x1 i 2 i x2 i

I;calc ;calc ;calc ;calc I II II where xI , xI , xI , xII are the experimental 1i , x2i , x1i , x2i and x1i 2i 1i 2i and calculated mole fractions, respectively. The tting parameters

14

B. Gonzlez et al. / J. Chem. Thermodynamics 60 (2013) 914 [16] F.S. Oliveira, M.G. Freire, P.J. Carvalho, J.A.P. Coutinho, J.N.C. Lopes, L.P.N. Rebelo, I.M. Marrucho, J. Chem. Eng. Data 55 (2010) 45144520. [17] J.A. Riddick, W.B. Bunger, T.K. Sakano, Organic Solvents, Wiley, New York, 1986. [18] T.M. Letcher, N. Deenadayalu, J. Chem. Thermodyn. 35 (2003) 6776. [19] S. Corder, E.J. Gonzlez, N. Calvar, . Domnguez, J. Chem. Thermodyn. 53 (2012) 6066.

[9] A.L. Revelli, F. Mutelet, J.N. Jaubert, J. Chem. Eng. Data 56 (2011) 38733880. [10] A.B. Pereiro, J.M.M. Arajo, J.M.S.S. Esperana, I.M. Marrucho, L.P.N. Rebelo, J. Chem. Thermodyn. 46 (2012) 228. [11] S. Corder, B. Gonzlez, J. Chem. Thermodyn. 55 (2012) 138143. [12] R.G. Seoane, E.J. Gonzlez, B. Gonzlez, J. Chem. Thermodyn. 53 (2012) 152 157. [13] S. Corder, B. Gonzlez, N. Calvar, E. Gmez, Fluid Phase Equilibr. 337 (2013) 1117. mez, N. Calvar, E.J. Gonza lez, E.A. Macedo, A. [14] R.G. Seoane, S. Corder, E. Go Domnguez, Ind. Eng. Chem. Res. 51 (2012) 24922504. [15] H. Renon, J.M. Prausnitz, AlChE J. 14 (1968) 135144.

JCT 12-671