The anodic oxidation of silver electrodes in NaOH solution and the reduction of the silver oxides formed were studied by potential step chronoamperometry. Oxidation of Ag to Ag20 is a diffusion-controlled reaction, the diffusion control being established in the solid phase. Oxidation of Ag20 to AgO proceeds via a nucleation and growth-controlled process. The amount of AgO decreased with increasing step height. The current--time curves for this reaction have been analysed with the Kolmogoroff--Avrami equation. Reduction of AgO to Ag20 occurs initially on the outside of the electrode, and the rate of the reaction is limited by diffusion of ions across the thickening layer of Ag20. Reduction of Ag20 to Ag proceeds via a nucleation and growth reaction.
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