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Mechanism of Water Oxidation by Ferrate(VI) at pH 7–9
Author(s) -
Chen Gui,
Lam William W. Y.,
Lo PoKam,
Man WaiLun,
Chen Lingjing,
Lau KaiChung,
Lau TaiChu
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201803757
Subject(s) - chemistry , protonation , intramolecular force , kinetics , reaction mechanism , spectrophotometry , inorganic chemistry , phosphate , rate determining step , photochemistry , catalysis , stereochemistry , ion , chromatography , organic chemistry , physics , quantum mechanics
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.