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DOI: 10.1039/A700722A (Paper) Reference Section for: J. Chem. Soc., Faraday Trans., 1997, 93, 2537-2544

Kinetics and mechanism of the oxidation of dimethyl sulfide by hydroperoxides in aqueous medium Study on the potential contribution of liquid-phase oxidation of dimethyl sulfide in the atmosphere

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Peter Amels, Horst Elias and Klaus-Jürgen Wannowius

Abstract

Conventional and multi-wavelength stopped-flow spectrophotometry has been used to study the kinetics of the oxidation of dimethyl sulfide (DMS) by hydroperoxides, ROOH=hydrogen peroxide (H2O2), peroxo formic acid (HCO3H), peroxo acetic acid (CH3CO3H), peroxo nitrous acid (ONOOH), peroxo monosulfuric acid anion (PMS=HSO5-), and the H2O2 analogue hypochlorous acid (HOCl), in aqueous solution in the pH range 0–14 at 293 K and I=1.0 M. The reaction between DMS and ROOH and between dimethyl sulfoxide (DMSO) and ROOH is a second-order process, leading to DMSO and dimethyl sulfone (DMSO2), respectively. It was shown by gas chromatography that, except for the oxidant ONOOH, DMSO and DMSO2 are the only oxidation products. It follows from the pH dependence of the second-order rate constant k2 that both the hydroperoxide ROOH, rate constant kROOH, and its anion ROO-, rate constant kROO, oxidize DMS and DMSO, respectively. The data for kROOH (dm3 mol-1 s-1) and for kROO (dm3 mol-1 s-1) at 293 K for the formation of DMSO and DMSO2 are presented. For the oxidation of DMS kROOH>kROO; for the step DMS→DMSO, kROOH ranges from 4780 (PMS) to 0.018 (H2O2), whereas kROO lies in the range 88 (PMS) to 0.0018 (H2O2); for the step DMSO→DMSO2, kROOH ranges from 349 (HOCl) to 2.7×10-6 (H2O2), whereas kROO lies in the range 18 (PMS) to 8.4×10-5 (H2O2). A mechanistic interpretation of the oxidation reactions, based on the ambifunctional character of both ROOH and DMSO, is presented. The relevance of in-cloud oxidation of DMS by atmospheric hydroperoxides such as CH3CO3H and HCO3H is discussed and substantiated.

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