Peroxymonosulfate decomposition

Thompson, R. (1981). Catalytic decomposition of peroxymonosulfate in aqueous perchloric add by dual catalysts. Inorg. Chem. 20,1005-1010. 

In addition to the S(IV) —H202 reaction, the reactions of other peroxides such as peroxymonosulfate, peroxyacetic acid, and methyl hydroperoxide with S(IV) are also sensitive to specific-acid catalysis (Hoffmann and Calvert, 1985). The rate of oxidation of S(IV) by HSO / is comparable to the rate of oxidation of S( IV) by hydrogen peroxide (Betterton and Hoffmann, 1988). We have proposed a general mechanism for the ROOH-S(IV) reaction in which the rate-determining step involves the acid-catalyzed decomposition of a peroxide-bisulfite intermediate. The rate expression applicable for this mechanism is... 

Scheme 3.62 Pathways a-k (a) nucleophilic addition of the ketone by peroxymonosulfate (b) formation ofthe oxy-anion intermediate (c) formation of the dioxirane (d) epoxidation of an olefin by the dioxirane (e) epimerization of the stereogenic centers of the ketone (f) hydration of the ketone (g) self-decomposition of peroxymonosulfate (h) Baeyer-Villiger oxidation (i) consumption of the dioxirane by peroxymonosulfate (j) self-decomposition ofthe dioxirane. (k) racemic epoxidation of the olefin by peroxymonosulfate itself...

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