Journal
INORGANIC CHEMISTRY
Volume 57, Issue 16, Pages 10189-10198Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b01386
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Funding
- National Natural Science Foundation of China [21773304]
- Fundamental Research Funds for the Central Universities [2015XKZD09]
- Natural Science Foundation of Jiangsu Province [BK20171186]
- Hungarian Research Fund NKFIH-OTKA [K116591]
- Higher Education Institutional Excellence Programme of the Ministry of Human Capacities in Hungary [20765-3/2018/FEKUTSTRAT]
- European Union - European Social Fund [EFOP-3.6.1.-16-2016-00004]
- [GINOP-2.3.2-15-2016-00049]
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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.
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