Realisation D'Une Electrode Indicatrice D'Ions Oxyde Dans Les Sels Fondus Au Moyen D'Electrolytes Solides

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Abstract
Solid solutions of CaO in ZrO2, are ionic conductors. Conduction involves oxide ion (O−-) vacancies in the crystal lattice. Membranes of such materials are selectively permeable to the ion O−-. Taking advantage of this remarkable feature, a novel “oxide indicator electrode” has been developed for measurements in a fused sodium-potassium chloride solvent in a range of temperatures between 720 and 800°C. The potential response was in concordance with the applicable Nernst Equation when the melt was basic, i. e., “rich” in O−- In “acidic” melts, deviations from the Nernst Equation were apparent due to contributions of anionic (chloride) conductance. Using our indicator electrode, sodium oxide was successfully titrated to a potentiometric end point by precipitation with coulometrically generated Cu+ and Ni++: the relevant solubility products of cuprous and nickelous oxide have been evaluated as 10−12.4 and 10−9.6, respectively, at 1000°K.

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