The Thermal Power of the Solid Electrolytes Ag[sub 4]MI[sub 5] and of Molten Mixtures of the Same Composition

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Abstract
Measurements are reported of the thermal power with reversible silver electrodes of polycrystalline samples of and of molten mixtures of the same composition . The Wagner‐Pitzer approximation for the entropy of a single ion is extended to molten mixtures and to nonbinary solid compounds and is used to calculate the heterogeneous contribution to the thermal power of . Then the heat of transport of Ag+ in solid may be calculated and is found to be 2.1 kcal mole−1. The term for molten is found to be 3.2 kcal mole−1. This same term is estimated from the variation of the homogeneous thermal power with temperature to be for the rubidium mixture, for the potassium mixture, and for the cesium mixture. The self‐consistency of the results and the agreement between the heat of transport in solid and the activation energy for diffusion (of Ag+) support the use of the extended form of the Pitzer equation.

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