Abstract
For the first time, the time dependence of the amount of O2 evolved in the reaction of Fe2+ with H2O2 (the Fenton reaction) was measured by following the decrease of the total [Fe3+] formed upon quenching the reaction mixture with an excess of a strongly acidic solution of Fe2+. The disappearance of Fe2+ in the reaction was followed by quenching it with o-phenanthroline and measuring the absorbance of the Fe2+-phenanthroline complex formed at λ=510 nm. At [H2O2]<10-4 mol dm-3, and quenching the reaction with Fe2+ ions, the formation of a new intermediate was observed. It was identified as the mixed valence binuclear species {FeOFe}5+. A new mechanism for the reaction has been proposed in which FeO2+ acts as the key intermediate. Several rate constants and ratios of rate constants have been determined. The existence of free radicals in the system does not seem to be compatible with the data.
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