Abstract
The kinetics of oxidation of diethyl sulfide (Et2S) with hydrogen peroxide (H2O2) in aqueous solutions of acetonitrile (MeCN) was studied using a kinetic distribution method. It was found that the order of the reaction with respect to the substrate depends on pH and changes from the first at pH 8.06 to nearly zero at pH 11.02. The initial rates of Et2S consumption increase with pH and linearly depend on the concentrations of the hydroperoxide anion (HOO–) and MeCN. It was assumed that the reaction involves the nonequilibrium formation of peroxyimidate in the slow stage of the interaction of HOO– with MeCN followed by the rapid oxidation of Et2S.
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Notes
According to Gillitt et al. [17], we hypothesized that the additives of MeCN do not have a significant effect on Ka.
As demonstrated previously [6], an increase in the solubility of Et2S in aqueous alcohol solutions makes it possible to compensate increase in the reaction rate constants and provide a high rate (W = k[Et2S]l of its oxidation.
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Translated by V. Makhlyarchuk
Abbreviations and designations: RSR', organic sulfides; MeCN, acetonitrile; RCN, nitriles; ArSMe, aryl methyl sulfides; Et2S, diethyl sulfide; PH, hydrogen peroxide; PI, activated form of Н2О2, peroxyimidic acid MeC(O2H)=NH2 or peroxyimidate MeC(O2H)=NH–; GLC, gas–liquid chromatography; KDM, kinetic distribution method.
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Liubymova, A.K., Bezbozhnaya, T.V. & Lobachev, V.L. Activation of Hydrogen Peroxide by Acetonitrile in the Oxidation of Thioethers: Reaction Kinetics and Mechanism. Kinet Catal 62, 342–349 (2021). https://doi.org/10.1134/S002315842103006X
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DOI: https://doi.org/10.1134/S002315842103006X