Thermodynamics of organic mixtures containing amines. IV. Systems with aniline

Abstract

Binary mixtures of aniline with benzene, toluene, alkane, alkanol, or N,N-dialkylamide have been investigated in the framework of the DISQUAC model. The reported interaction parameters change regularly with the molecular structure of the mixture components. The model consistently describes a set of thermodynamic properties including liquid–liquid equilibria, vapor–liquid equilibria, and molar excess enthalpies. The two latter properties for ternary systems are well-represented by DISQUAC using binary parameters only (i.e., neglecting ternary interactions). A comparison of DISQUAC results and those obtained from the UNIFAC (Dortmund version) and ERAS models is also shown. The experimental molar excess enthalpies for binary and ternary mixtures are better described by DISQUAC than by UNIFAC. ERAS fails when representing molar excess enthalpies of those binary systems including methanol or ethanol. This may be due to the existence of strong dipolar interactions among aniline molecules as well as to effects related to the equation of state term, evaluated comparing molar excess enthalpies, and molar excess internal energies at constant volume. The study of the aniline systems in terms of the concentration–concentration structure factor also underlines the importance of dipolar interactions in solutions with alkanes or alcohols, which may be due to the high polarizability of the aniline molecule.Key words: thermodynamics, mixtures, aniline, dipolar interactions, structural effects.