Kinetics and mechanism of silver(I)-catalysed oxidation of malonic acid by peroxodiphosphate in acetate buffers

Summary The kinetics of the silver(I)-catalysed oxidation of malonic acid by peroxodiphosphate (pdp) was studied in acetate buffers. The rate law as represented by-dpdp]/dt = {(k ₁ K _inf2 ^sup-1 H⁺]² + k ₂H⁺] + k ₃ K ₃)/ (H⁺]²/K ₂ + H⁺] + K ₃)}pdp]Ag(I)] conforms to the proposed mechanism. The rate is independent of malonic acid concentrations. Acetate ions do not affect the rate; however, the rate decreases as the ionic strength increases. A probable portrait of reaction events is suggested. A comparative analysis of the reactivity pattern of malonic acid towards peroxodiphosphate and peroxodisulphate in presence of silver(I) has been made.