Kinetics of the Two-Stage Oxidation of Sulfide by Chlorine Dioxide
Kinetics of the Two-Stage Oxidation of Sulfide by Chlorine Dioxide
复制标题
二氧化氯两阶段氧化硫化物的动力学
DOI：
10.1021/acs.inorgchem.8b01386
复制
发表时间：
2018-08-20
影响因子：
4.6
通讯作者：
Horvath, Attila K.
中科院分区：
文献类型：
--
作者：
Cseko, Gyorgy;Pan, Changwei;Horvath, Attila K.
The sulfide chlorine dioxide reaction was found to have two distinct kinetic stages at alkaline conditions. The first stage proceeds so rapidly that it can only be measured by a stopped-flow technique at low temperature and leads to the parallel formation of polysulfide and sulfate as sulfur-containing products. At the same time, chlorite, chlorate, and chloride are produced from chlorine dioxide in detectable amounts, suggesting a complex stoichiometry. A nine-step kinetic model including short-lived intermediates like sulfide radical and *HSClO2- is proposed to describe the kinetic data in this rapid stage. In an excess of chlorine dioxide, the first stage is followed by a significantly slower one to be measured by conventional UV vis spectroscopy at room temperature. Considering that tetrasulfide is formed during the first rapid course of the reaction, the subsequent slow kinetic stage can only be described by the direct oxidation of tetrasulfide by chlorine dioxide and, surprisingly, the tetrasulfide-catalyzed disproportionation of chlorine dioxide.
