A reaction mechanism has been validated for the photochemical generation of hydroxyl radicals by ultraviolet or visible irradiation of oxalato iron(III) complexes (ferrioxalate) in the presence of hydrogen peroxide and 2-propanol as a model substrate. A kinetic simulation program incorporating the set of reactions was written to predict the behavior of this photochemical system. The program calculates the quantum yield of oxidation of 2-propanol used as a hydroxyl radical scavenger. The scavenger's oxidation product, 2-propanone, was analyzed by gas chromatog raphy after controlled exposure of the solution to a calibrated light source. The theoretical quantum yields of 2-propanol oxidation, ΦRH, agreed reasonably well with experimentally determined ΦRH values under a variety of initial reaction conditions. The value of ΦRH, which under appropriate conditions is directly proportional to the quantum yield for the generation of hydroxyl radicals, ΦOH, was considerably greater than unity in most cases (often ...
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