The oxidation of dissolved sulfur dioxide at platinum supported in porous graphite sheet electrodes was investigated between 450 and 750 mV (RHE) using a variety of platinum loadings and SO2 concentrations. Controlled reductive pretreatment of these porous electrodes in the presence of SO2 was found to produce catalytic effects which resulted in enhanced steady-state oxidation currents due to formation of a sulfur-modified platinum surface. In hybrid cells with fuel cell-type oxygen gas diffusion cathodes operating in the electrogenerative (galvanic) mode, the pretreated platinumgraphite anodes were used to oxidize 3-500 mM SO2 in 3M H2SO4. Performance of the anodes, which contained 0.3-18 mg Pt/cm 2, was shown to be consistent with kinetic control by a mechanism similar to those postulated from earlier studies of the reaction at bulk platinum. Pretreatment appears to enhance the rate of the electron transfer steps without affecting that of a preceding chemical step. The pretreatment effect is not limited to graphite-supported platinum electrodes and seems to be general for SO2 oxidation at high surface area platinum anodes.The electrochemical oxidation of sulfur dioxide is of practical interest because of potential applications such as waste gas clean-up with sulfuric acid recovery (1-4) and possible use in energy conversion cycles (5, 6). Work here is a continuation of earlier investigations into the electrogenerative anodic oxidation of sulfur dioxide and possibilities for improving performance. Recently, we described how the reduction of adsorbed sulfur dioxide at porous, platinum-black gas diffusion electrodes produced catalyst modifications which altered selectivity considerably both in the course of ethanol oxidation and of nitric oxide reduction (7-10). Similar electrodes were studied for anodic oxidation of gaseous SO2 (11, 12) but a quantitative effect of pretreatment was not identified.Anodic oxidation of dissolved sulfur dioxide at bulk precious metal electrodes has been the subject of several investigations into the effect of electrochemical pretreatments on voltammetric behavior (13)(14)(15)(16)(17)(18)(19)(20). Enhancement of anodic current (activation) was observed after certain pretreatments which involved controlled reduction in the presence of dissolved sulfur dioxide. Few of these studies investigated steady-state performance of activated electrodes (17-19) while earlier studies with high surface area electrodes (1, 2, 5, 21) did not address the effect of pretreatment on SO2 oxidation rate. Thus, it was of special interest to explore the effect of a reductive pretreatment on the steady-state operation of working cells converting SO~ to sulfuric acid with high surface area electrodes.An interesting, early description of pretreatment procedures and their effects on anodic oxidation of SO2 at bulk platinum is found in papers by Seo and Sawyer (13,22). Using 1-10 mM SO2 in 0.1M H2SO4, they found that cycling the electrode potential between -0.15 and +1.5 V vs. SCE resulted in enhanced and more re...