Electron Spin Resonance Studies of Reactions of Photo-generated Organic Radicals with Hydrogen Peroxide in Aqueous Solution

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Abstract
The reactions with H2O2 of free radicals derived from 2-propanol, methanol, dimethoxymethane, and tetrahydrofuran have been investigated by e.s.r. using in-cavity photolysis with acetone photosensitization to generate the radicals in flowing aqueous solutions. The variation in the concentrations of the radicals derived from a particular solute with addition of H2O2 is attributed to the selective oxidation of one radical by H2O2, propagating a secondary chain reaction, e.g.,[Formula: see text]The rate constant for the oxidation of the acetone ketyl radical ((CH3)2ĊOH) by H2O2 is estimated to be 5 × 105 M−1 s−1.The results and conclusions of this study are demonstrated to be consistent with the results of previous investigations employing γ-radiation, photolysis, and the reaction of Ti(III) with H2O2 for initiation.Results are also reported for the direct photolysis of aqueous malonic acid in the presence of H2O2.

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