Mechanism of Water Oxidation by Ferrate(VI) at pH 7–9
Gui ChenSchool of Environment and Civil Engineering Dongguan University of Technology Guangdong 523808 P.R. ChinaWilliam W. Y. LamDepartment of Chemistry and Institute of Molecular Functional Materials City University of Hong Kong Tat Chee Avenue Hong Kong P.R. ChinaPo‐Kam LoDepartment of Chemistry and Institute of Molecular Functional Materials City University of Hong Kong Tat Chee Avenue Hong Kong P.R. ChinaWai‐Lun ManDepartment of Chemistry Hong Kong Baptist University Waterloo Road Kowloon Tong Kowloon, Hong Kong P.R. ChinaLingjing ChenSchool of Environment and Civil Engineering Dongguan University of Technology Guangdong 523808 P.R. ChinaKai‐Chung LauDepartment of Chemistry and Institute of Molecular Functional Materials City University of Hong Kong Tat Chee Avenue Hong Kong P.R. ChinaTai‐Chu LauDepartment of Chemistry and Institute of Molecular Functional Materials City University of Hong Kong Tat Chee Avenue Hong Kong P.R. China
2018en
ABI
Annotatsiya
Abstract The kinetics of water oxidation by K 2 FeO 4 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 4 2− ] and [H + ]. These results are consistent with a proposed mechanism in which the first step involves the initial equilibrium protonation of FeO 4 2− to give FeO 3 (OH) − , which then undergoes rate‐limiting O−O bond formation. Analysis of the O 2 isotopic composition for the reaction in H 2 18 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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