The Lead Dioxide Anode. II. The Kinetics and Participation of the Lead Dioxide Electrode in Electrochemical Oxidation Reactions in Sulfuric Acid

Lead dioxide is a strong oxidizer in sulfuric acid, consequently electrochemical oxidation of solution species at a lead dioxide anode may occur by a two-step, C-E process (chemical oxidation of solution species by PbO2 followed by electrochemical regeneration of the reduced lead dioxide surface). The maximum rate of each step has been determined in sulfuric acid for specified lead dioxide surfaces and compared with the rates observed for the electrochemical oxidation of cerium(III) and manganese(II) on the same electrode surfaces. While the rate of electrochemical oxidation of a partially reduced PbO2 surface may be sufficient to support the observed rates of CeIII and MnII oxidation at the lead dioxide anode, the rate of chemical reaction between PbO2 and the reducing species is not. Hence it is concluded that the lead dioxide electrode functions as a simple, 'inert' electron-transfer agent during the electrochemical oxidation of CellI and MnII in sulfuric acid. In general, it will most probably be the rate of the chemical step which determines the feasibility or otherwise of the C-E mechanism.