Abstract
The reversible heat effects of half‐cell processes have been measured in a twin calorimeter consisting of a Dewar flask divided into two halves by means of a vertical partition. Both compartments contain the same electrolyte and each has an electrode. A hole in the partition, covered by filter paper, permits the passage of electrolytic current between the compartments. The total heat effect and the heat due to irreversible phenomena are measured separately for each compartment. The difference between these two gives the desired reversible heat.The half‐cells studied include copper in acid copper sulfate, silver in acid silver perchlorate, and silver‐silver chloride in various chloride solutions. The effect of “transport entropies” on these measurements is outlined. Presently accepted theories of the “irreversible” or “steady‐state” thermodynamics of electrolytic cells predict the equivalence of half‐cell entropy data obtained by the present calorimetric method and data obtained from thermocell studies. This predicted agreement was not obtained in the case of the half‐cell silver‐silver perchlorate.
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