A Potential-Induced Transformation in the Double Electrical Layer on the Rhenium Electrode in Alkali Chloride Melts.

Abstract

Structural transformations in the adsorption layer caused by an electric potential are investigated using the experimental data on the capacitance of a double electric layer for a rhenium electrode in molten sodium, potassium and cesium chlorides at 1093 K. Likening the double electric layer to a flat capacitor, as well as the effective length of the shielding of the electrode charge and changes in the charge sign depending on the applied potential are estimated. It is found that near the minimum potential of the capacitance curve, the shielding length decreases proportionally to the square of the potential due to the deformation of the double layer. The deformation reaches critical values at the potentials of −0.65, −0.38 and −0.40 V for the Re|NaCl, Re|KCl and Re|CsCl systems respectively, and decreases sharply at more positive potentials. The analysis of the dependence of the charge density on the electrode revealed the effect of shielding of potential-induced rhenium cations by salt phase anions. The strong Raman-active Re–Cl stretching mode was observed at 292 cm−1. This can be explained by the transfer of anions across the interface resulting in the formation of ordered layers of ion associations (possibly, ReXn(n − 1)−) on a positively charged surface.