Anodic Charging of Electrodes at Low Temperatures Studied by Electron Spin Resonance

Abstract
A study of anodic oxidation processes at several electrodes at low temperatures in KOH solutions is presented. The techniques of electron spin resonance have been used to identify intermediates. From a detailed kinetic analysis of the information obtained, the role of the formation and decay of O3and certain metallic oxide radicals in the anodic charging of metal (hydr)oxide electrodes has been deduced.The formation of O3 and/or O2, or neither, during anodic oxygen evolution seems to be controlled by the tightness of binding of OH to the surface (hydr)oxide which changes with the metal in the (inferred) order of increasing binding strength Cd, Pb, Ni, Pt.Once formed in solution, O3&([a-z]+); decays slowly below 0 °C, slower the higher the KOH concentration. Primary dissociation, influenced by ion pair formation and by hydrolysis, controls the rate.

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