Thermodynamic Properties of Metal‐Water Systems at Elevated Temperatures

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Abstract
The advent of commercial nuclear power generation has created an increased need for thermodynamic data on metal‐water systems at temperatures up to 350°C. The entropy correspondence principle discovered by Criss and Cobble [J. Am. Chem. Soc., 86, 5385 and 5391 (1964)] provides an excellent means of estimating high‐temperature partial molar ionic entropies and hence high‐temperature heat capacities, from entropy values at 25°C. It is therefore often possible to calculate both equilibrium constants and standard electrode potentials with surprising accuracy for elevated temperatures. Unfortunately, different conventions have been used by several authors in publishing calculated numerical data. One purpose of the present paper is to clarify these differences. In addition, a means of simplifying the calculations is described. This new approach permits rapid modification or augmentation of existing values when more accurate data become available, or when information at other temperatures is required. Values of , the ionization product of water, and , the standard electrode potentials of silver‐silver halide electrodes, are calculated as examples for temperatures up to 300°C, and these values are compared with available experimental data.

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