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Thermodynamic Properties of Dimethyl Sulfoxide + Benzene Or + Isopropylbenzene Mixtures

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Thermodynamic Properties of Dimethyl Sulfoxide + Benzene Or + Isopropylbenzene Mixtures THERMODYNAMIC PROPERTIES OF DIMETHYL SULFOXIDE + BENZENE OR + ISOPROPYLBENZENE MIXTURES Latifa Negadi*,**, Ahmed Ait Kaci***, Jacques Jose** * Université Abou-Bakr Belkaid de Tlemcen, Faculté des Sciences, Département de Chimie, BP 119, Tlemcen 13000 (Algeria). [email protected]. ** LICAS, Laboratoire de Chimie Analytique I, Université Claude Bernard - Lyon I. 43, Bd du 11 Novembre 1918. Villeurbanne Cedex 69622 (France). *** Laboratoire de Thermodynamique des Mélanges Organiques, Université des Sciences et Technologies Houari Boumédiène, Dar El Beïda, Alger 16111 (Algeria). ABSTRACT The vapor pressure of binary mixtures of dimethyl sulfoxide + benzene or + isopropyl benzene and of the three pure components were measured by means of a static apparatus at temperatures between 293.15 K and 363.15 K. Molar excess Gibbs energies GE were calculated for several constant temperatures, and fitted to a third- order Redlich-Kister equation. Calorimetric excess enthalpy HE measurements for the binary mixtures are also reported at 298.15 K. The data on excess molar Gibbs energies and excess molar enthalpies are examined on the basis of the DISQUAC and Modified UNIFAC group contribution models which provide a fairly consistent description of phase equilibria and the related excess functions. Keywords: Vapor-liquid equilibria; Excess enthalpy; DISQUAC; UNIFAC; Dimethyl sulfoxide. INTRODUCTION The present paper is part of a research program on vapor-liquid equilibria (VLE) and excess enthalpies HE in mixtures of strongly polar non hydrogen bonded compounds with saturated, unsaturated, and aromatic hydrocarbons [1-7]. The purpose of the present work is to investigate VLE and excess enthalpy HE in binary mixtures of dimethyl sulfoxide + benzene or + isopropylbenzene and to examine the applicability of the DISQUAC and modified UNIFAC models to the results. A survey of the literature [8-11] shows that no VLE data are available for dimethyl sulfoxide + isopropylbenzene mixture. Dimethyl sulfoxide + benzene has been investigated isothermally by Kenttämaa et al. [12,13] and Heinrich [14]. Excess enthalpies, HE, for dimethyl sulfoxide + benzene have been measured by Absood et al. [15], Fenby et al. [16], Kenttämaa et al. [13] and Tanaka [17]. For dimethyl sulfoxide + isopropylbenzene, no calorimetric data are available except molar enthalpies of solution at infinite dilution of isopropylbenzene, as well as benzene, in dimethyl sulfoxide [18,19]. EXPERIMENTAL TECHNIQUE The experimental vapor pressure, P, data were taken with an apparatus described in detail by Blondel-Telouk et al. [20,21], as a function of the temperature, T, for given constant values of the mole fraction composition, xi. The apparatus allows measurements in the P range from 27 Pa to 200 103 Pa and from 258.15 to 468.15 K. Vapor pressures are measured by means of pressure gauges (Rosemount, Model 1151 DPE 22S2, Minneapolis, Minn., USA), protected by a differential pressure indicator (MKS, Model 615D, MKS Instruments, USA). The pressure gauges were checked periodically by means of a Hg or oil manometer and a Bouty (Paris, France) Type 70298 cathetometer, readings accurate to within 1 Pa. Temperature of oil thermostat was maintained constant to within 0.01 K and was measured by means of a copper-constantan thermocouple calibrated against a Leeds and Northrup standard Pt resistance thermometer 8163-B, provided with the National Bureau of Standards (Washington D.C., USA) certificate, and connected to Mueller type G2 bridge (precision 10-4W). All temperatures are on ITS-90. The estimated uncertainties in P and T are, respectively: σ(P) = 0.15 P (if P/Pa < 13.3), σ(P) = 0.05 P (in the range 13.3 < P/Pa < 200), σ(P) = 0.005 P (in the range 200 < P/Pa < 1000), σ(P) = 0.002 P (in the range 1000 < P/Pa < 200 103), and σ(T) = 0.01 K. Mixtures were prepared by mass and thoroughly degassed by distillation as described by Blondel-Tellouk et al. [20,21]. The final composition of the liquid was determined after each measurement of P by GLC on a column filled with Carbowax as stationary phase, using a thermal conductivity detector. The experimental HE data were taken at atmospheric pressure by means of a microcalorimeter, model C 80II (SETARAM, Lyon, France). The temperature T (ITS- 90) was maintained constant at (298.15 ± 0.02) K. Check measurements on cyclohexane + heptane are in agreement to within 2 % (over the entire range of concentration) with the data reported by Marsh [22]. The estimated uncertainties in E E the mole fraction composition xi and H are, respectively, σ(xi) = 0.0002 and σ(H ) = 5 J mol-1. MATERIALS The chemical substances were supplied by Janssen Chimica (Geel, Belgium) and Aldrich Chem. (Milwaukee, WI, USA) and were used without further purification. The mole fraction purities, tested by GLC, were: dimethyl sulfoxide (Jassen, > 99 %), benzene (Janssen, ~ 99 %) and isopropylbenzene (Aldrich, > 99 %). RESULTS Table 1 lists, for the pure components dimethyl sulfoxide, benzene and isopropylbenzene, the vapor pressures measured in this work, between 293.15 K ad 363.15 K, together with the molar volumes extrapolated from the densities [23-27] and the second molar virial coefficients estimated by the method of Tsonopoulos [28,29] using the literature data for acentric factor and critical properties of pure compounds [23-27]. Our vapor pressure data for the pure liquid components agree with those reported in the literature [30-33] Table 2 gives, for dimethyl sulfoxide + benzene or + isopropylbenzene mixtures, experimental data for total vapor pressures at different temperatures together with the corresponding compositions of the liquid and vapor phases, the activity E coefficients γ1 and γ2, and the values of the excess molar Gibbs energies G calculated by Barker's method [34], using the Redlich-Kister equation (1) m E j-1 G(1)= x1 x2 ∑ R T Gj (x1 - x2 ) j = 1 where x1 is the molar fraction for dimethyl sulfoxide Table 3 lists the values Gj for the two binary mixtures. All binary mixtures exhibit positive deviations. The equimolar GE of dimethyl sulfoxide + benzene increases with increasing temperature from 804 J mol-1 (293.15 K) to 850 J mol-1 (363.15 K). The equimolar GE of dimethyl sulfoxide + isopropylbenzene is almost independent from temperature, 1325 J mol-1 at 293.15 K and 1336 J mol-1 at 363.15 K (Figures 1 and 2). Our excess Gibbs energy, GE, for dimethyl sulfoxide + benzene, at 298.15 K agree to within 2 % with literature data [12, 14]. Table 1 : Molar volumes V* (10-6 m3 mol-1), vapor pressures P* (kPa) and second molar virial Coefficients, Bii (10-6 m3 mol-1) for pure compounds. T (K) Dimethyl sulfoxide Benzene Isopropylbenzene V* P* Bii V* P* Bii V* P* Bii 293.15 71.0 0.056 -6422 88.9 10.029 -1624 139.5 0.456 -5151 298.15 71.4 0.082 -5870 89.4 12.707 -1543 140.2 0.622 -4802 303.15 71.7 0.115 -5386 89.9 15.946 -1469 140.9 0.838 -4491 313.15 72.3 0.224 -4583 91.0 24.452 -1340 142.2 1.472 -3963 323.15 73.0 0.414 -3952 92.1 36.312 -1230 143.7 2.481 -3535 333.15 73.7 0.733 -3449 93.2 52.403 -1135 145.1 4.030 -3182 343.15 74.5 1.248 -3043 94.4 73.714 -1053 146.7 6.332 -2887 353.15 75.6 2.054 -2711 95.7 101.332 -980 148.3 9.659 -2637 363.15 76.8 3.276 -2436 97.0 136.436 -916 149.9 14.340 -2424 Experimental molar excess enthalpies HE of the binary mixtures are listed in Table 4. The results have been fitted to the smoothing equation: n - 1 E i H(2)i, exp = x1 (1 - x1) ∑ H i (2x1 - 1) i = 0 E The values of the coefficients Hi and the standard deviations σ(H ) are given by : N 1/ 2 E E E 2 σ(H ) = ∑ (Hi,exp −Hi,calc ) / (N - n) (3) i = 1 where N is the number of experimental points and n the number of coefficients Hi; they are determined by least-square analysis and are reported in Table 5. The molar excess enthalpy, HE, of dimethyl sulfoxide + isopropylbenzene is considerably larger than for dimethyl sulfoxide + benzene, due to the partially aliphatic character of isopropylbenzene (Figure 3). Our HE data for dimethyl sulfoxide + benzene at 298.15 K are in good agreement with those reported by Kenttämaa et al. [13]. Table2 : Values of the vapor pressure P (Pa), standard deviations δP/P (%), activity E -1 coefficients γ1 and γ2 and excess molar Gibbs energies G (J mol ). E T(K) x1 y1 P δP / P γ1 γ2 G Dimethyl sulfoxide (1) + benzene (2) 293.15 0,1114 0,0022 9325,2 0,55 3,2621 1,0388 403,4 0,2165 0,0031 8823,4 -0,04 2,1943 1,1208 632,5 0,3197 0,0037 8361,9 -0,23 1,7154 1,2252 757,3 0,4107 0,0044 7911,0 -0,02 1,4767 1,3349 805,1 0,5132 0,0052 7288,3 0,00 1,3009 1,4879 800,6 0,6260 0,0064 6493,1 0,41 1,1675 1,7171 729,1 0,7400 0,0084 5343,0 -0,56 1,0754 2,0498 586,0 0,8362 0,0121 4040,2 0,36 1,0271 2,4311 409,2 0,9060 0,0196 2636,9 -0,10 1,0079 2,7592 250,0 298.15 0,1114 0,0025 11803,8 0,51 3,2147 1,0381 404,8 0,2165 0,0035 11162,8 -0,04 2,1746 1,1189 635,1 0,3197 0,0043 10569,1 -0,22 1,7048 1,2219 760,7 0,4107 0,0050 9993,2 0,00 1,4695 1,3302 808,8 0,5132 0,0060 9196,1 0,00 1,2961 1,4813 804,1 0,6260 0,0074 8178,3 0,39 1,1646 1,7067 732,0 0,7400 0,0097 6715,3 -0,55 1,0740 2,0321 588,0 0,8362 0,0139 5065,6 0,37 1,0266 2,4031 410,4 0,9060 0,0225 3301,0 -0,10 1,0078 2,7209 250,6 303.15 0,1114 0,0028 14799,8 0,46 3,1694 1,0375 406,3 0,2165 0,0039 13988,7 -0,04 2,1557 1,1171 637,8 0,3197 0,0048 13232,7 -0,22 1,6945 1,2187 764,1 0,4107 0,0057 12503,9 0,02 1,4627 1,3257 812,5 0,5132 0,0068 11493,7 0,00 1,2916 1,4748 807,7 0,6260 0,0084 10204,1 0,37 1,1619 1,6965 735,0 Table 2 (continued) E T(K) x1 y1 P δP / P γ1 γ2 G Dimethyl sulfoxide (1) + benzene (2) 0,7400 0,0110
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