Experimental and predicted vapour–liquid equilibrium of 1,4-dioxane with cycloalkanes and benzene

doi:10.1016/j.fluid.2005.09.010

Fluid Phase Equilibria

Volume 238, Issue 1, 25 November 2005, Pages 1-6

https://doi.org/10.1016/j.fluid.2005.09.010 Get rights and content

Abstract

Isobaric vapour–liquid equilibrium measurements for mixtures containing 1,4-dioxane and cyclopentane, cyclohexane or benzene at the pressures of 40.0, 66.6 and 101.3 kPa are reported. The experimental data were tested for thermodynamic consistency, the calculated activity coefficients have been correlated using Wilson, NRTL and UNIQUAC equations. The system 1,4-dioxane with cyclohexane shows minimum temperature azeotropes. Using our VLE results UNIFAC and predictive Soave–Redlich–Kwong methods were tested.

Introduction

We present here isobaric vapour–liquid equilibrium measurements at the pressures of 40.0, 66.6 and 101.3 kPa for the binary mixtures 1,4-dioxane with cyclopentane, cyclohexane or benzene. In a previous paper [1] we have reported isobaric VLE measurements for the same mixtures with 1,3-dioxolane instead of 1,4-dioxane.

There are some works involving isothermal vapour–liquid equilibrium for 1,4-dioxane with cyclohexane [2], [3], [4], [5], [6] and benzene [7], [8], [9], [10], but as far as we know there are not references for isobaric VLE studies on the systems presented here.

For each mixture, the results have been checked for thermodynamic consistency and the corresponding activity coefficients have been calculated and correlated with Wilson [11], NRTL [12] and UNIQUAC [13] models.

Besides from this experimental work we have used our results to verify the accuracy of the VLE prediction of modified UNIFAC [14] and predictive Soave–Redlich–Kwong (PSRK) [15] methods. The VLE predictions with the modified UNIFAC method are satisfactory while when the PRSK method is used the predictions are far worse, however the predictions with the later method can be improved by using in the g^E mixing rule calculations the modified UNIFAC method instead of the original UNIFAC method.

Section snippets

Materials

The liquids used were 1,4-dioxane, cyclohexane and benzene (better than 99.9%) supplied by Aldrich and cyclopentane (better than 99.0%) obtained from Fluka. The purity of the chemicals was checked by gas chromatography and by comparing the measured densities and normal boiling points with those reported in the literature [16], this comparison is shown in Table 1. No further purification was considered necessary.

Methods

The still used to study the vapour–liquid equilibrium was an all-glass dynamic

Results and discussion

The vapour–liquid equilibrium data, T, x₁ and y₁, along with the calculated activity coefficients, γ_i, are gathered in Table 3. The activity coefficients of the components in the liquid phase were calculated from the following equations: $γ_{i} = \frac{y_{i} P}{x_{i} p_{i}^{o}} exp [\frac{(B_{i i} - V_{i}^{o}) (P - p_{i}^{o}) + {(1 - y_{i})}^{2} P δ_{i j}}{R T}]$ where $δ_{i j} = 2 B_{i j} - B_{i i} - B_{j j}$ where x_i and y_i are the liquid- and vapour-phase compositions, P is the total pressure, $p_{i}^{o}$ are the vapour pressures of the pure compounds calculated with the Antoine equation, where the constants

VLE predictions

The group contribution methods can be used to predict phase equilibria when experimental data are not available, the most successful of these methods is the modified UNIFAC [14] because it is continuously revised and enlarged [23]. In this work we have tested the accuracy of the VLE predictions of the modified UNIFAC method. The temperature and vapour-phase composition obtained experimentally were compared with the predictions using modified UNIFAC method, in Table 8 the average deviations in

Acknowledgements

The authors are grateful to Diputación General de Aragón for financial assistance. A. Villares, M. Haro and B. Giner thanks the pre-doctoral grants from M. E. C. and M. C. Y. T.

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Experimental and predicted vapour–liquid equilibrium of 1,4-dioxane with cycloalkanes and benzene

Abstract

Introduction

Section snippets

Materials

Methods

Results and discussion

VLE predictions

Acknowledgements

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Fluid Phase Equilibr.

Chem. Eng. Sci.

Phys. Chem. Liq.

Z. Anorg. Chem.

Int. Data Ser., Sel. Data Mixtures, Ser. A

J. Chem. Soc., Faraday Trans.

J. Chem. Eng. Data

J. Chem. Soc., Faraday Trans. I

J. Am. Chem. Soc.

J. Chem. Eng. Jpn.