Experimental kinetics of sulfide oxidation by hydrogen peroxide presents a pH-dependent profile. In this article, it was carried out a detailed study of the mechanism and kinetics of dimethyl sulfide (DMS) oxidation by H2O2 in neutral, acid, and basic aqueous medium using ab initio calculations. The results point out that DMS oxidation in neutral aqueous medium occurs through its direct reaction with H2O2. In acid medium, cluster-continuum model calculations shows that cluster is the best representation of the very reactive species. In basic medium, there is formation of the species. However, the pathway involving this species has high free energy barrier, making this pathway unfeasible. The theoretical pH-rate profile is in good agreement with the experimental observations. © 2013 Wiley Periodicals, Inc.

中文翻译：

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过氧化氢氧化二甲基硫醚的 pH 速率曲线预测：难以捉摸的 H3O2+Ion 的作用

过氧化氢氧化硫化物的实验动力学呈现出依赖于 pH 值的曲线。在本文中，使用 ab initio 计算详细研究了 H2O2 在中性、酸性和碱性水性介质中氧化二甲硫醚 (DMS) 的机理和动力学。结果表明，DMS 在中性水介质中的氧化是通过与 H2O2 直接反应而发生的。在酸性介质中，簇连续模型计算表明簇是反应性很强的物种的最佳代表。在基本介质中，有物种的形成。然而，涉及该物种的途径具有高自由能壁垒，使得该途径不可行。理论 pH 值曲线与实验观察结果非常一致。© 2013 威利期刊公司。