Abstract
The kinetic behaviour of the PbO 2 electrode is determined by three reactions: (i) deposition/dissolution of lead dioxide, (ii) changes in the stoichiometry of the oxide, especially by incorporation/dissolution of hydrogen; (iii) anodic evolution of oxygen. Immediately following commencement of current flow the stoichiometry-changing reaction predominates, because, we postulate, the proton transfer across the PbO 2/electrolyte phase boundary is almost uninhibited. Investigations of the kinetics of this reaction have therefore been carried out by means of current pulse measurements. Under appropriate conditions the current in the stationary state is used for PbO 2 deposition/dissolution only. Current-overvoltage curves for these reactions have been obtained from measurements with thin PbO 2 layers, where the stationary state was reached quickly.
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