Redox recipes. I. Reaction between ferrous iron and peroxides. General considerations

Abstract

AbstractVarious mechanisms which have been proposed for the reaction between ferrous iron and hydrogen peroxide are reviewed. Two of these mechanisms appear equally satisfactory on the basis of present evidence: that of Bray and Gorin, involving formation of tetravalent (ferryl) iron, and that of Haber and Weiss, involving formation ofhydroxyl and perhydroxyl radicals. Mechanisms involving these intermediates have been developed for the ferric iron‐catalyzed decomposition of hydrogen peroxide; the mechanism of Bray and Gorin appears satisfactory, while that of Haber and Weiss leads to certain inconsistencies. A mechanism with ferrous iron and hydroxyl and perhydroxyl radicals as intermediates is presented, which accounts for the experimental observations in the ferric iron‐catalyzed decomposition of hydrogen peroxide. The reaction between hydrogen peroxide and ferrous iron induces the reaction between hydrogen peroxide and various organic compounds; this induced reaction (termed a Fenton reaction) is a chain reaction which is initiated by the active intermediates (ferryl iron or hydroxyl radical) formed in the primary reaction. The determination of hydrogen peroxide by reaction with ferrous iron, if carried out in the presence of various organic compounds (termed promoters), gives incorrect results, due to induced oxidation of the promoters; other compounds, termed suppressors, reduce the extent of this induced oxidation of promoters. It appears that both types of compounds react with ferryl iron or hydroxyl radical to form radicals, which if formed from promoters, reduce ferric iron or hydrogen peroxide, while the radicals formed from suppressors oxidize ferrous iron. These considerations are of particular importance in the determination of organic hydroperoxides. The reaction between hydrogen peroxide or organic peroxides and ferrous iron can induce, or initiate, the polymerization of vinyl monomers; this is an example of redox polymerization, which is of considerable practical importance at present.