Thermal and volumetric properties of chloroform+benzene mixtures and the ideal associated solution model of complex formation

Abstract

In the ideal associated solution model, activity coefficients of all species (labelled A, B, and AB here) are taken to be unity at all mole fractions and all temperatures, with several derivative consequences that have not previously been investigated. We have applied this model to an analysis of the thermodynamic properties (vapor pressures, excess volumes, excess enthalpies, partial molar enthalpies of solution, and excess heat capacities) of the chloroform + triethylamine system in terms of K, ΔV⊖, ΔH⊖, and ΔCp⊖ for the equilibrium represented by A+B=AB. It is shown that there is good consistency between the relatively simple chemical ideal associated solution model and all available thermodynamic data except heat capacities, for which the consistency between model and data is less good. Some limitation of the ideal associated solution model are discussed, along with the relationship of this model to hydrogen bonding in the AB complex and to spectroscopic investigations. New thermal (partial molar enthalpies of solution and excess heat capacities) and volumetric data are presented.