Abstract

It has been shown that emf measurements on galvanic cells involving solid-sulphide electrolytes may yield valuable thermodynamic data. CaSY 2S 3 and CaSZrS 2 solid solutions were expected to satisfy the conditions as solid electrolyte. Emf measurements on the cells MoMo 2S 3(3 + s)/electrolyte/CuCu 2S(1 + 1) (I), MoMo 2S 3(s + s)/electrolyte/Fe FeS(s + 1) (II), MoMo 2S 3(s + s)/electrolyte/WWS 2(s + s) (III), WWS 2(s + s)/electrolyte/CuCu 2S(1 + 1) (IV), and WSW 2(s + s)/ electrolyte/FeFeS(s + 1) (V) have been made using sulphide sensors in the temperature range 1000–1285°C. Observed emf values were compared with those calculated from the H 2H 2S gas equilibrium investigations. The sensor tubes were also dipped into liquid copper with sulphur concentration from 0.43 to 1.06 at% 1180–1312°C and the emf data were checked by the values deduced from the gas equilibrium experiments.

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