Research Initiation: Development of a Thermodynamic Perturbation Theory for Electrolyte Solutions

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An equation of state of aqueous electrolyte solutions at finite concentrations is developed in this work. The approach is based upon a new thermodynamic perturbation theory in which the reference fluid is taken to be a mixture of neutral and charged spheres. Interactions arising from solvent polarity are treated as the perturbation. The properties of the new reference fluid are obtained from numerical solutions of the Ornstein-Zernicke integral equation using finite element methods. The direct correlation function for charged pairs is approximated by the HNC equation and PY closure used for other pairs. The accuracy of these correlation functions are tested by comparison with computer simulations. This basic research is required in the development of a predictive description of electrolyte solution thermodynamics and phase equilibria. The work is partially motivated by a continuing interest in the application of statistical mechanics to the description of fluid interfaces. Aside from the role played in the development of interfacial science, a predictive description of ionic solutions is urgently needed for the synthesis and optimization of industrial processes, for the description of chemically complex aqueous environments, and for an understanding of some biological systems.