New statistical mechanical model for calculating Kirkwood factors in self-associating liquid systems and its application to alkanol+cyclohexane mixtures

Abstract

A new statistical mechanical model for calculating Kirkwood factors in self-associating molecular liquids and their mixtures with nonassociating components has been developed in a consistent way which is based on an extended version of the Flory-Huggins model taking into account chemical association equilibria. The majority of molecular parameters involved into the theory has been fixed by independent quantum mechanical ab initio calculations of associated molecular clusters. The model is also able to predict other thermodynamic mixture properties such as the enthalpy of mixing and also the infrared absorbance of monomer alcohol species as function of concentration. Experimental results of nine alcohol+cyclohexane mixtures taken from the literature have been used to test the new model. The Kirkwood correlation factor gK, the molar enthalpy of mixing HmE, and the monomer IR absorbance can be described simultaneously in excellent agreement with experimental data covering the whole range of mole fraction including temperature dependence of gK, HmE, and the IR absorbance. Two parameters have been adjusted freely for each system. A third parameter for the nonspecific intermolecular dispersion interactions has been adjusted within a limited range of possible values given by physical arguments. The model opens a new way of a more reliable understanding of structures and equilibrium properties of hydrogen bonded systems in the condensed liquid state.