The kinetics and mechanism of the ferrate(VI) oxidation of hydroxylamines
The kinetics and mechanism of the ferrate(VI) oxidation of hydroxylamines
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DOI：
10.1021/ic020705x
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发表时间：
2003-10-20
影响因子：
4.6
通讯作者：
Hornstein, BJ
中科院分区：
文献类型：
--
作者：
Johnson, MD;Hornstein, BJ
高铁酸钾（VI）的水溶液干净且快速地将羟胺氧化成一氧化二氮，将N-甲基羟胺氧化成亚硝基甲烷，将N-苯基羟胺氧化成亚硝基苯，以及将O-甲基羟胺氧化成甲醇和氮气。动力学显示相对于每个反应物的一级行为和代表酸依赖和独立途径的两个术语组件。提出了一个一般的机制，涉及中间体的形成加上一个两电子氧化。
Aqueous solutions of potassium ferrate(VI) cleanly and rapidly oxidize hydroxylamine to nitrous oxide, N-methylhydroxylamine to nitrosomethane, N-phenylhydroxylamine to nitrosobenzene, and O-methylhydroxylamine to methanol and nitrogen. The kinetics show first-order behavior with respect to each reactant and a two term component representing acid dependent and independent pathways. A general mechanism involving intermediate formation coupled with a two-electron oxidation is proposed.