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Mechanism of oxidation of diphenyl sulfide by peroxyanions
Author(s) -
Srinivasan C.,
Kuthalingam P.,
Arumugam N.
Publication year - 1982
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550141007
Subject(s) - chemistry , peroxydisulfate , redox , homolysis , sulfide , protonation , photochemistry , reaction rate , hydrolysis , reaction mechanism , radical , sulfoxide , medicinal chemistry , inorganic chemistry , organic chemistry , ion , aqueous solution , catalysis
Abstract Reactions of diphenyl sulfide with the two oxidants peroxydisulfate and peroxydiphosphate are described. With each oxidant, the reaction is first order in the oxidant and zero order in the substrate. The rate of the reaction is also independent of the effect of the substituent. Hydrogen ion catalyzes the reactions. The lack of inhibition of the reaction rate by added acrylamide rules out the possibility of a radical reaction initiated by the homolysis of the peroxyanions. From the effect of [H + ] on the oxidation rates, the active species involved in the reactions have been determined. The redox reaction is essentially proceeding via hydrolysis of the protonated peroxy anions in a rate‐determining step, followed by a fast step involving the oxidation of diphenyl sulfide to diphenyl sulfoxide. This has been confirmed by estimating the hydrolyzed products in each case and also by the product analyses.