Abstract
AbstractThe kinetics of dimethyl sulfoxide (DMSO) oxidation by peroxomonophosphoric acid (PMPA) in aqueous medium at 308 K and I = 0.4 mol/dm3 follow the rate expressions equation image In the pH range from 0 to 2, where k1 and k2 are 5.092 × 10−1 dm3/mol sec and ≃ 0, respectively; equation image in the pH range from 4 to 7, where k2 = 8.127 × 10−3 and k3 = 2.90 × 10−3 dm3/mol sec; and equation image in the pH range from 10 to 13.6, where k4 ≃ 0, and k5 = 3.08 × 10−2 dm3/mol sec.The reaction is interpreted in terms of mechanisms involving an electrophilic and a nucleophilic attack of the peroxomonophosphoric acid species, respectively, in acid and alkaline regions, on the sulfur atom of the sulfoxide molecule giving rise to S‐type transition states followed by oxygen‐oxygen bond fission to form the products.
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