The Kinetics of the Potentiostatic Oxidation of Lead Sulfate Films on Lead in Sulfuric Acid Solution

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Abstract
Models, proposed by Pavlov and Ruetschi to describe the multiphase electrode structure of anodically oxidized lead/sulfuric acid solutions, have been quantitatively tested, modified, and elaborated in accordance with the experimental evidence. The current, during oxidation at constant potential in the region of lead dioxide formation, is shown to be controlled sequentially by at least three diffusion processes, followed by at least two electrocrystallization stages and further intervals of diffusion control. The natures and concentrations of the diffusing species are quantitatively characterized on the basis of kinetic and thermodynamc data. The corresponding values of pH in the electrode pores are calculated. A reversal of the pH gradient in the pores apparently occurs in close association with the onset of production. It is following this stage of the anodic oxidation that the charging kinetics become qualitatively dependent on temperature. At normal temperatures, growth of at the expense of lead sulfate occurs. At very low temperatures this process is blocked, resulting in poor subsequent charge acceptance.

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