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.

中文翻译：

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乙腈在硫醚氧化中活化过氧化氢：反应动力学和机理

摘要

使用动力学分布方法研究了乙腈 (MeCN) 水溶液中二乙硫醚 (Et ₂ S) 与过氧化氢 (H ₂ O ₂ ) 的氧化动力学。发现相对于底物的反应顺序取决于 pH 值，并从 pH 8.06 的第一个变化到 pH 11.02 时几乎为零。Et ₂ S 消耗的初始速率随 pH 值而增加，并且线性取决于氢过氧化物阴离子 (HOO ^– ) 和 MeCN的浓度。这是假设该反应涉及HOO的相互作用的慢阶段非平衡形成peroxyimidate的^-用MeCN，随后的Et迅速氧化₂ S.