Thermodynamics of complex formation in chloroform + 1,4-dioxane

Abstract

We have made new measurements of excess heat capacities and excess volumes of mixtures of chloroform and dioxane. In combination with published vapor pressures and excess enthalpies the results have been analyzed using the ideal associated solution model to yield K, ΔHθ, ΔCpθ, and ΔVθ for the formation of AB and A2B complexes. It is demonstrated that the ideal associated solution model is consistent with all of the available thermodynamic data for this system, indicating that chemical interactions of the two components can account for nearly all of the deviations from ideal solution behavior. The results of our thermodynamic analysis are discussed in relation to the results of similar analyses of other systems in which there are strong chemical interactions of chloroform with electron-donor molecules. Keywords: complex formation, hydrogen bonding, ideal associated solution model, chloroform, 1,4-dioxane.