Elsevier

Fluid Phase Equilibria

Volume 310, Issues 1–2, 25 November 2011, Pages 56-62
Fluid Phase Equilibria

Liquid–liquid equilibria for systems of water + methanol + methyl anthranilate at several temperatures

https://doi.org/10.1016/j.fluid.2011.07.008Get rights and content

Abstract

Liquid–liquid equilibria (LLE) data for the systems of water + methyl anthranilate and water + methanol + methyl anthranilate were measured under atmospheric pressure over the temperature range of 298.15–323.15 K. Phase diagrams were obtained by determining solubility and tie-line data. The reliability of the experimental tie-line data was determined through the Bachman plots. The data were correlated using the NRTL and UNIQUAC models. Average RMSD obtained from the UNIQUAC and NRTL model were 0.0082 and 0.135, respectively. The correlated results were in agreement with the experiment data, though the average deviations from the UNIQUAC model are slightly smaller than those from the NRTL model.

Highlights

► We measure LLE data for two systems including methyl anthranilate. ► We determine the reliability of experimental tie-line data through Bachman plots. ► We use the NRTL and UNIQUAC models to correlate the experimental data. ► The correlated results are in agreement with the experiment data. ► Average deviations from UNIQUAC are slightly smaller than those from NRTL.

Introduction

Methyl anthranilate (MA) is a very important chemical intermediate used as an artificial flavor and scent in foods and cosmetics [1], [2], [3], [4]. It is also a safe repellent against birds [5], [6], [7], [8] in agriculture and an intermediate in the saccharin production process. A number of procedures to produce methyl anthranilate have been reported [4], [9], [10]. The current practice is to use various acids as catalysts in the manufacture of methyl anthranilate either starting with isatoic anhydride and methanol or by the esterification of anthranilic acid with methanol [11]. Though most of MA could be separated from reaction mixtures by traditional separation methods, a part of methanol and MA still remain in the large quantity of waste water generated in the reaction. In recent years, MA has received increasing attention [12], [13]. It is known that LLE data are essential for the design of extraction equipment and/or for the calculation of the thermodynamic limit of a given separation. However, to our knowledge, with respect to the liquid–liquid equilibria data of the systems including MA, no literature data were available.

The purpose of this work is to measure LLE data for the systems of water + MA and water + methanol + MA under atmospheric pressure over the temperature range of 298.15–323.15 K. The experimental tie-line data were correlated to test consistency with the Bachman equations [14]. The NRTL [15] and UNIQUAC [16] models were used to correlate the experimental data for the systems studied in the research. The influence of methanol on the mutual solubility of MA and water was discussed. The experimental data provide a basis for influence of methanol on the mutual solubility of MA and water, which can serve for separation and processes design in industrial applications.

Section snippets

Materials

All chemicals were purchased from Tianjin Reagent Company (China), and distilled water was used. MA was dried using molecular sieves with a pore diameter of 0.5 nm and purified by vacuum distillation processing. The purity of the chemicals was examined using an Agilent 6820 gas chromatography. No impurity peaks were detected. Densities were measured with Anton Paar density meter (Model 4500). Refractive indexes were measured with an Abbe refractometer with an accuracy of ±5 × 10−4. The measured

Results and discussion

At liquid–liquid equilibrium, the composition of two phases can be determined from the following Eqs. (1), (2):(γixi)1=(γixi)2xi1=xi2Here γi1 and γi2 are the corresponding activity coefficients of component i in phases 1 and 2, xi1 and xi2 are the mole fractions of component i in the system in phases 1 and 2, respectively. The calculation procedure was detailed in Walas [21].

Bachman correlation Eq. (3) was used to ensure the quality of the obtained experimental tie-line data.w32=A+Bw32w11

Conclusion

Liquid–liquid equilibrium data for the systems of water + MA and water + methanol + MA were measured under atmospheric pressure in the temperature range of 298.15–323.15 K. It was observed that the temperature has a slight influence on the size of the immiscibility region for the system of water + methanol + MA in the investigated temperature range. The LLE data were correlated using the NRTL and UNIQUAC activity coefficient models. Regarding the system water + methanol + MA, the UNIQUAC and NRTL models

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