Liquid-Liquid Equilibria for Systems Containing 4-Phenylbutan-2-one or Benzyl Ethanoate and Selected Alkanes

TL;DR

This study investigates liquid-liquid equilibria for specific aromatic and ester mixtures with alkanes, revealing how molecular interactions and chain length influence phase behavior, and validates the DISQUAC model's predictive accuracy.

Contribution

It provides new LLE phase diagrams for aromatic and ester systems with alkanes and demonstrates the effectiveness of the DISQUAC model in predicting these equilibria.

Findings

LLE phase diagrams show upper critical solution temperatures increasing with chain length.

Aromatic interactions are stronger than linear molecules due to proximity effects.

DISQUAC model accurately predicts critical compositions, temperatures, and curve shapes.

Abstract

Liquid-liquid equilibrium (LLE) phase diagrams have been determined, by means of the critical opalescence method with a laser scattering technique, for the mixtures 4-phenylbutan-2-one + CH$_3$(CH$_2$)$_n$CH$_3$ ($n = 10,12,14$) and for benzyl ethanoate + CH$_3$(CH$_2$)$_n$CH$_3$ ($n = 12,14$). The systems are characterized by having an upper critical solution temperature (UCST), which increases with n. The corresponding LLE curves show a rather horizontal top and become skewed toward higher mole fractions of the polar compound when n is increased. Calorimetric and LLE measurements show that, for mixtures with molecules with a given functional group, interactions between aromatic molecules are stronger than those between homomorphic linear molecules (aromaticity effect). This has been ascribed to proximity effects arising from the presence of the polar group and the aromatic ring within the same molecule. Proximity effects become weaker in the sequence 1-phenylpropan-2-one > 4-phenylbutan-2-one > 1-phenylethanone and are more important in benzyl ethanoate than in ethyl benzoate molecules. Values of the critical compositions and temperatures calculated with the DISQUAC group contribution model are in good agreement with the experimental results. Accordingly, the shape of the LLE curves is also correctly described by DISQUAC.