A kinetic and ESR investigation of iron(II) oxalate oxidation by hydrogen peroxide and dioxygen as a source of hydroxyl radicals

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J S Park, P M Wood, Michael Jonathan Davies, B C Gilbert, A C Whitwood

The reaction of Fe(II) oxalate with hydrogen peroxide and dioxygen was studied for oxalate concentrations up to 20 mM and pH 2-5, under which conditions mono- and bis-oxalate complexes (Fe[II](ox) and Fe[II](ox)2[2-]) and uncomplexed Fe2+ must be considered. The reaction of Fe(II) oxalate with hydrogen peroxide (Fe2+ + H2O2 --> Fe3+ + .OH + OH-) was monitored in continuous flow by ESR with t-butanol as a radical trap. The reaction is much faster than for uncomplexed Fe2+ and a rate constant, k = 1 x 10(4) M(-1) s(-1) is deduced for Fe(II)(ox). The reaction of Fe(II) oxalate with dioxygen is strongly pH dependent in a manner which indicates that the reactive species is Fe(II)(ox)2(2-), for which an apparent second order rate constant, k = 3.6 M(-1) s(-1), is deduced. Taken together, these results provide a mechanism for hydroxyl radical production in aqueous systems containing Fe(II) complexed by oxalate. Further ESR studies with DMPO as spin trap reveal that reaction of Fe(II) oxalate with hydrogen peroxide can also lead to formation of the carboxylate radical anion (CO2-), an assignment confirmed by photolysis of Fe(II) oxalate in the presence of DMPO.

Original languageEnglish
JournalFree Radical Research
Volume27
Issue number5
Pages (from-to)447-58
Number of pages12
ISSN1071-5762
Publication statusPublished - Nov 1997

    Research areas

  • Cyclic N-Oxides, Electron Spin Resonance Spectroscopy, Ferrous Compounds, Hydrogen Peroxide, Hydrogen-Ion Concentration, Hydroxyl Radical, Kinetics, Oxalates, Oxalic Acid, Oxidation-Reduction, Oxygen, Spin Labels, Spin Trapping, tert-Butyl Alcohol

ID: 138284996