Excess enthalpies and isothermal (vapour + liquid) equilibria of (1-methyl-2-pyrrolidone + 1-chloroalkane or +α,ω-dichloroalkane) mixtures

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Abstract

Excess enthalpies HmE at T = (298.15 and 308.15) K have been measured for liquid (1-methyl-2-pyrrolidone + 1-chlorobutane, or +1-chlorohexane, or +1-chlorooctane, or +1,2-dichloroethane, or +1,4-dichlorobutane, or +1,6-dichlorohexane) and isothermal (vapor + liquid) equilibria (VLE) at T = (313.15, 323.15, and 333.15) K are reported for (1-methyl-2-pyrrolidone + 1-chlorobutane, or +1-chlorohexane, or +1,2-dichloroethane). The VLE data were reduced using the Redlich–Kister equation taking into consideration the vapour-phase imperfection in terms of 2nd molar virial coefficients.

Introduction

The thermodynamic behaviour of mixtures containing amides is of considerable interest, not only because of the high polarity of these compounds [1] but also because they contain both the amino and the carbonyl group being used as simple models in biochemistry [2]. In this work we have studied the thermodynamic behaviour of a cyclic amide, 1-methyl-2-pyrrolidone in a polar medium which is different from water. The polar compounds used as second component are 1-chloroalkanes [3] or α,ω-dichloroalkanes [4] used widely in chemical industry as intermediates or final products.

Following with our studies on the thermodynamics of binary liquid mixtures containing amides and haloalkanes [5], [6], we report here the excess enthalpy HmE, at T = (298.15 and 308.15) K, for liquid (1-methyl-2-pyrrolidone + 1-chlorobutane, or +1-chlorohexane, or +1-chlorooctane, or +1,2-dichloroethane, or +1,4-dichlorobutane, or +1,6-dichlorohexane) and the isothermal (vapor + liquid) equilibria (VLE), at T = (313.15, 323.15, and 333.15) K, for (1-methyl-2-pyrrolidone + 1-chlorobutane, or +1-chlorohexane, or +1,2-dichloroethane).

As far as we know, the only previous measurements on these mixtures are those for (1-methyl-2-pyrrolidone + 1,2-dichloroethane): HmE at T = 298.15 K and the isobaric (vapour + liquid) equilibrium at 95.3 kPa [7].

Section snippets

Materials

1-Methyl-2-pyrrolidone (better than 99 mol% pure) and 1-chlorobutane (better than 99.8 mol% pure) were obtained from Riedel-de Häen. 1-Chlorooctane (better than 98 mol% pure), 1,2-dichloroethane (better than 99.5 mol% pure), and 1,4-dichlorobutane (better than 97 mol% pure) were supplied from Fluka AG Buchs, and 1-chlorohexane (better than 99.0 mol% pure) and 1,6-dichlorohexane (better than 98 mol% pure) were obtained from Aldrich Chem. Co. All the liquids were used without further purification.

In

Results and discussion

The experimental HmE values, at T = (298.15 and 308.15) K, are collected in table 2 and are plotted as a function of the mole fraction, at T = 298.15 K, in figure 1. These results are fitted using the Redlich–Kister equation,Hm,calcEx1(1-x1)J·mol-1=Aj(2x1-1)j-1,where N is the total number of measurements and n is the number of coefficients Aj.

The coefficients Aj and the standard deviation calculated as follows:σ(HmE)=(HmE-Hm,calE)/(N-n)1/2,where N is the total number of measurements and n is the

Acknowledgements

P. García-Giménez acknowledges the financial support received by D.G.A, Departamento de Educación y Ciencia and the European Social Fund (B020/2003).

The authors are grateful for the financial assistance of D.G.A. to the G.E.T.T.A Group of research.

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