The reduction of I2 by hydrogen peroxide, a primary water radiolysis product, has been identified as a key reaction that would influence iodine volatility in nuclear reactor accident conditions (13). Although there have been a number of studies of the reduction of I2, there exists a great degree of controversy regarding the intermediates involved, the effect of buffers, and the general rate law (19). Because the rates and the mechanism of this reaction are important in predicting the pH dependence of iodine behaviour in reactor containment building after a postulated reactor accident, we have undertaken a kinetic study of I2 reduction by H2O2 in aqueous solution over a pH range of 69. The experiments were performed using stopped-flow instrumentation and monitoring the decay of I3 spectrophotometrically. The effects of buffer catalysis have been examined by comparison of kinetic data obtained in sodium barbital (5,5-diethylbarbituric acid), disodium citrate, and disodium hydrogen phosphate buffers. The effect of buffers, combined with the complex acid dependence of the rate law, explains many of the discrepancies reported in earlier literature.Key words: hydrogen peroxide, molecular iodine, kinetics, iodine volatility.
