Oxidations at Sulfur Centers by Aqueous Hypochlorous Acid and Hypochlorite: Cl+ Versus O Atom Transfer
| Autor: | Ying Hu, Guangyuan Xie, David M. Stanbury |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Tetrathionate
Thiosulfate Aqueous solution Hypochlorous acid 010405 organic chemistry Inorganic chemistry chemistry.chemical_element Hypochlorite 010402 general chemistry 01 natural sciences Medicinal chemistry Sulfur 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound chemistry Thiourea Sulfite Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry. 56:4047-4056 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | Sulfur-containing compounds are known to be susceptible to oxidation by aqueous HOCl, but the factors affecting the rates of these reactions are not well-established. Here we report on the kinetics of oxidation of thiosulfate, thiourea, thioglycolate, (methylthio)acetate, tetrathionate, dithiodiglycolate, and dithiodipropionate at 25 °C and 0.4 M ionic strength. These reactions obey the general rate law −d[OCl–]/dt = (kOCl–[OCl–] + kHOCl[HOCl])[substrate] with some exceptions: tetrathionate and the two disulfides undergo rate-limiting hydrolysis at high pH, and dithiodiglycolate has an additional term in the rate law that is second order in [substrate]. The reactions of HOCl are believed to have a Cl+ transfer mechanism, and in the case of thiosulfate the rate of hydrolysis of the ClS2O3– intermediate was determined. In the case of thiourea evidence was obtained for thiourea monoxide as a long-lived product. It is shown that sulfite and species with terminal sulfur atoms have kHOCl values in the vicinity ... |
| Databáze: | OpenAIRE |
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