A pulse radiolysis study of the reactions of the hydrated electron and hydroxyl radical with the oxalate ion in neutral aqueous solution |
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Authors: | B. G. Ershov E. Janata M. S. Alam A. V. Gordeev |
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Affiliation: | (1) Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119991, Russia;(2) Hahn-Meitner Institut Berlin GmbH, Glienicker strasse 100, D-14109 Berlin, Germany |
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Abstract: | The rate constants of the reactions of e aq ? and the OH· radical with the oxalate ion in a neutral aqueous solution were measured by means of the pulse radiolysis technique. They were found to be (3.5 ± 0.5) × 107 and (1.5 ± 0.2) × 107 l mol?1 s?1, respectively. The radical anion ?OOC-C·OO2? is characterized by an optical absorption band that has a maximum at 270 nm and a molar absorption coefficient of (2400 ± 200) l mol?1 cm?1. The radical anion ·OOC-COO?, the product of the reaction with the OH· radical, exhibits absorption that has no maximum and increases in intensity with a decrease in the wavelength extending to the UV region (?220 = 1800 l mol?1 cm?1). The mechanism of radiation-chemical transformations in aqueous oxalate solutions is discussed. |
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