Thermodynamics of Redox and Solubility Equilibria Based on Hydration and Partial Dissociation of Electrolytes

Authors: Raji Heyrovska

Thermodynamic treatments of properties of strong electrolytes in aqueous solutions based on the idea of complete dissociation and activity coefficients became too complicated to be meaningful. Therefore, on systematically re-investigating the existing data, it became evident that the earlier ideas of partial dissociation and hydration were correct. The degrees of dissociation and hydration numbers evaluated from vapor pressures or osmotic coefficients could explain many thermodynamic properties quantitatively (from zero to saturation for electrolytes like NaCl). This paper presents simple thermodynamic relations for redox and solubility equilibria in terms of ionic molalities and hydration. Lewis and Randall’s results for a classical electrochemical cell have been used for demonstrating the new approach.

Comments: 19 pages, 2 figures

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Submission history

[v1] 2017-10-29 10:35:56

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