The Kinetics of the Oxidation of Halide Ions by Monosubstituted Peroxides

Effects of chloride ions on bleaching of azo dyes by Co2+/oxone regent: Kinetic analysis

“…It is likely that PMS would directly react with chloride to generate active chloride species that cause dye decoloration. In fact, the potential of forming active chlorine species from monosubstituted peroxides such as oxone has been known in the early study [29][30][31][32]. However, Fortnum et al [29] and Narender et al [31] reported that the rates of active chlorine formation are extremely low (1.35 × 10 −3 M −1 s −1 ) when oxone is used without Co activation as compared to those obtained when a radical mechanism operated.…”

Kinetic and mechanistic studies on the oxidation of nitrite by peroxomonophosphoric acid

“…Thus the active species of nitrite can be established to be HN02 only. Further the parallelism of the reactivity of the different PMPA species, namely, H3P05, HzPO,, and HPOg-, with linearly decreasing electrophilicity [lo] order indicates a polar mechanism, preferably an electrophilic attack by the PMPA species on the nucleophilic center of the nitrite (that is, the nitrogen atom with its lone pair), as in the case of other nucleophiles like alkyl sulfides [7], amines [10,11], and halides [12,13] by PMPA. It is interesting to note that H202, CH3C03H, and HSO; react with nitrite by similar mechanisms [2].…”

Oxidation studies with peroxomonophosphoric acid. II. A kinetic and mechanistic study of dimethyl sulfoxide oxidation in acid and alkaline media

“…This is quite in agreement with the earlier observations [lo-131 wherein the peroxide has been shown to act as an electrophile in the acidic oxidations of sulfoxides. Thus it can be inferred that and 2.90 X the oxidation of DMSO in the acidic pH region involves a rate-determining electrophilic attack on the sulfur atom of the sulfoxide molecule by the PMPA species, resulting in transition states [I, 11, and 111 corresponding to steps (4), (5), and (6), respectively], followed by oxygen-oxygen bond fission to give dimethyl sulfone and phosphoric acid.…”

“…Recently Ogata and co-workers [3,4] have reported the oxidation of some organic compounds with PMPA and have stressed the occurrence of an ionic mechanism in the reaction. In the kinetics of oxidation of halide ions [5] by peroxomonophosphoric acid, peroxomonosulfuric acid, and peroxoacetic acid, and of iodide ions [6] by peroxomonophosphoric acid, various protonated species of the peroxo compounds have been shown to participate in the oxidation process. In view of the fact that sulfoxide can act as an electrophile or as a nucleophile under different circumstances, we have initiated the study of the oxidation of dimethyl sulfoxide (DMSO) by PMPA over the pH ranges from 0 to 2, 4 to 7, and 10 to 14, which is presented in this article.…”