The kinetics of water oxidation by K FeO has been reinvestigated by UV/Vis spectrophotometry from pH 7-9 in 0.2 m phosphate buffer. The rate of reaction was found to be second-order in both [FeO ] and [H ]. These results are consistent with a proposed mechanism in which the first step involves the initial equilibrium protonation of FeO to give FeO (OH) , which then undergoes rate-limiting O-O bond formation. Analysis of the O isotopic composition for the reaction in H O suggests that the predominant pathway for water oxidation by ferrate is intramolecular O-O coupling. DFT calculations have also been performed, which support the proposed mechanism.
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