Chatterjee, Debabrata and Shome, Sanchari and Jaiswal, Namita and Moi, S.C. (2014) Mechanism of the oxidation of thiosulfate with hydrogen peroxide catalyzed by aqua-ethylenediaminetetraacetatoruthenium(III). Journal of Molecular Catalysis A: Chemical, 386. pp. 1-4.

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Catalytic ability of [RuIII(edta)(H2O)]− (edta4− = ethylenediaminetetraacetate) complex toward oxidation of thiosulfate (S2O32−) in presence of H2O2 has been explored in the present work. The kinetics of the catalytic oxidation of thiosulfate (S2O32−) has been studied spectrophotometrically as a function of [RuIII(edta)], [H2O2], [S2O32−] and pH. Spectral analyses and kinetic data indicate a catalytic pathway involving activation of both substrate (S2O32−) and oxidant (H2O2). Substrate activation pathway involves the formation of a red [RuIII(edta)(S2O3)]3− species through the reaction of the [RuIII(edta)(H2O)]− catalyst complex and the substrate (S2O32−). Hydrogen peroxide reacts directly with thiosulfate coordinated to the RuIII(edta) complex to yield sulfite as immediate oxidation product. Peroxide activation pathway is governed by the formation of [RuV(edta)(O)]− catalytic intermediate which oxidize thiosulfate, however, at slower rate (View the MathML source at 25 °C) as compared to the rate of oxidation of the coordinated thiosulfate (View the MathML source at 25 °C). Sulfite and sulfate were found to be the oxidation products of the above described catalytic oxidation process. A detailed mechanism in agreement with the spectral and kinetic data is presented.

Item Type: Article
Subjects: Chemistry
Depositing User: Dr. Sarita Ghosh
Date Deposited: 22 Sep 2016 10:11
Last Modified: 22 Sep 2016 10:11

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