Isobaric vapor–liquid equilibria for binary systems of butyl chlorides with heptane, toluene and cyclohexane at 101.3, 80.0 and 53.3 kPa

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Abstract

Isobaric vapor–liquid equilibrium (VLE) data are reported at 101.3, 80.0 and 53.3 kPa for six binary systems of 1-chlorobutane with heptane, cyclohexane and toluene, and 2-chlorobutane with the same hydrocarbons. The experimental isobaric T, x and y data were fitted to four two-parameter models namely Redlich–Kister, NRTL (α12 = 1), Wilson and UNIQUAC. The maximum likelihood principle was applied to adjust the model parameters.

Introduction

Earlier [1], [2], in an attempt to predict vapor–liquid equilibrium at constant temperature in mixtures containing chloroalkanes, we applied a theory termed Hard Sphere Expansion-Conformal Solution Theory (HSE-CST) [3]. This theory is a result of statistical thermodynamics. According to this theory, mixture properties are described in term of intermolecular potential function like the one proposed by Lennard–Jones, known as Lennard–Jones (12-6) potential function. In the modifications we have introduced, the Lennard–Jones (12-6) parameter, ɛ/k, was temperature dependent [4].

Vapor–liquid experimental data at constant pressure are needed to check this dependency. In this work, vapor–liquid equilibrium data of binary systems of 1-chlorobutane and 2-chlorobutane with heptane, toluene and cyclohexane were measured at three constant pressures namely 101.3, 80.0 and 53.3 kPa.

It should be pointed out that some of the investigated binary systems are available in the literature (particularly at 101.3 kPa). No experimental data are available in the literature for the same binary systems at 80.0 and 53.3 kPa.

Section snippets

Chemicals used

The chemicals were used directly without further purification. In Table 1 the sources and the purities of the chemicals used are listed. The normal boiling points obtained in this work are compared with those of literature [5]. The results are summarized in Table 2.

Apparatus

The apparatus used is an ebulliometer very similar to Othmer still [6]. The pressure is measured by means of a second ebulliometer (standard ebulliometer for pure compounds) [7] which is connected to the first one.

The standard

Pure compounds

For each pure component vapor pressure was measured at several temperatures. In Table 3 the direct experimental data are reported. The experimental vapor pressures versus temperatures were fitted to the well known Antoine equation:lnP(bar)=ABT(K)+C

The maximum likelihood procedure was applied to fit experimental PT data of pure compounds. In Table 4 the parameters AC of Antoine equation are listed together with standard deviations for pressure and temperature.

Binary mixtures

Isobaric vapor–liquid

Discussion

Normal boiling points of the pure components used in this study are in good agreement with the literature values as shown in Table 2, indicating that they are of good purity.

Application of the Van Ness–Byer–Gibbs thermodynamic consistency test [16] to all the six binary mixtures investigated in this work, established that the present experimental P, T, x and y measurements are thermodynamically consistent. In fact the distribution of deviations from fitted data agrees with Van Ness–Byer–Gibbs

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