Kinetics of the initial steps in the aqueous oxidation of thiosulfate by chlorine dioxide

The reaction of ClO2(•) with S2O3(2-) in aqueous solution is a component of the "crazy clock" reaction of ClO2(-) with S2O3(2-), and under conditions of excess S2O3(2-) the absorbance at 360 nm due to ClO2(•) decays with sigmoidal kinetics. A chain reaction mechanism is inferred on the basis that very small concentrations of SO3(2-) accelerate the reaction, and methionine inhibits the reaction. Pseudo-first-order kinetics is observed in the presence of relatively large methionine concentrations, leading to the simple rate law -d[ClO2]/dt = (ka[S2O3(2-)] + kb[S2O3(2-)](2))[ClO2], with ka = 452 ± 16 M(-1) s(-1) and kb = (5.7 ± 0.2) × 10(5) M(-2) s(-1) at 25 °C and pH 7.6. Under these conditions, the initial products are ClO2(-) and S4O6(2-). A classical electron-transfer mechanism is assigned to the reaction that occurs under conditions of methionine inhibition.