One- Versus Two-Electron Oxidation with Peroxomonosulfate Ion: Reactions with Iron(II), Vanadium(IV), Halide Ions, and Photoreaction with Cerium(III)

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University of Debrecen, Department of Inorganic and Analytical Chemistry, Debrecen 10, POB 21, Hungary, H-4010
* To whom correspondence should be addressed. E-mail: [email protected]. Tel: + 36 52 512-900/22373. Fax: + 36 52 489-667.
Cite this: Inorg. Chem. 2009, 48, 4, 1763–1773
Publication Date (Web):January 21, 2009
https://doi.org/10.1021/ic801569k
Copyright © 2009 American Chemical Society
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Abstract

The kinetics of the redox reactions of the peroxomonosulfate ion (HSO5) with iron(II), vanadium(IV), cerium(III), chloride, bromide, and iodide ions were studied. Cerium(III) is only oxidized upon illumination by UV light and cerium(IV) is produced in a photoreaction with a quantum yield of 0.33 ± 0.03. Iron(II) and vanadium(IV) are most probably oxidized through one-electron transfer producing sulfate ion radicals as intermediates. The halide ions are oxidized in a formally two-electron process, which most likely includes oxygen-atom transfer. Comparison with literature data suggests that the activation entropies might be used as indicators distinguishing between heterolytic and homolytic cleavage of the peroxo bond in the redox reactions of HSO5.

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Concentration dependence plots, ionic strength dependence plot, Eyring plots, and mathematical deductions of various equations. This material is available free of charge via the Internet at http://pubs.acs.org.

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