Electrochemical reactions at Pbo₂ electrodes. Part III. β-PbO₂ electrodes in acid perchlorate electrolytes at high overpotential

Abstract

The mechanism of exchange between β-lead dioxide and plumbous ions in solution has been investigated using the galvanostatic technique. Interpretation of the η D vs.i data is consistent with a change in mechanism from a single two-electron transfer step to two successive single-electron transfer steps as the magnitude of the potential excursion from equilibrium is increased.Analysis of the slopes obtained from the linear-logarithmic region indicates that the slow step in the reaction is that leading to the formation of a Pb(III) intermediate.The orders of reaction with respect to the plumbous and hydrogen ions have been obtained from the dependence of the rate of the reaction on the concentration of the electro-reactive species.A reaction mechanism is suggested on the basis of the kinetic data.