A study of the electrolytic solution process using the scaled particle theory. 5. Heat capacity of aqueous ions at elevated temperatures

Abstract

A theory composite of the scaled particle theory and the Born model of solvent continuum has been used to theoretically calculate the standard heat capacity of hydration as well as the partial molal heat capacity of aqueous ions and electrolytes at elevated temperatures. The uncertainties in the second temperature derivatives of solvent dielectric constant at various temperatures present a barrier to an accurate heat capacity prediction by the theory. Nevertheless, the agreement between the predicted standard heat capacity of electrolytes in solution and the corresponding experimental data, particularly at higher temperatures, is encouraging. Moreover, the composite theory seems to provide the most accurate thermodynamic predictions to date for aqueous electrolytes at higher temperatures without involving any arbitrary adjustable parameter. We therefore use this theory to find the proper ionic scale of the partial molal heat capacities at elevated temperatures. Key words: scaled particle theory, solvent continuum model of Born, standard heat capacity of aqueous ions, absolute scale for hydration thermodynamic quantities.