Reaction of ferrate (VI)/ferrate (V) with hydrogen peroxide and superoxide anion--a stopped-flow and premix pulse radiolysis study.

Abstract:

:The reduction of ferrate(VI) to ferrate(V) by superoxide ions was studied over the pH range 2.6-13.0 using the premix pulse radiolysis technique. The pH dependence indicates that only the unstable protonated forms of ferrate, H2FeO4 (pKa3.5) and HFeO4- (pKa7.3) are reactive, k(HFeO4(-) + O2) = (1.7 +/- 0.2) x 10(7) M-1 s-1. The stable ferrate ion, FeO4(2-), showed no significant reactivity towards either hydrogen peroxide or superoxide anion. The rate constants for the spontaneous dimerization and decomposition of the protonated ferrates, e.g. k(HFeO4(-) + HFe04) approximately 250 M-1s-1, are orders of magnitude slower than their corresponding reduction reduction by superoxide indicating an outer-sphere mode of electron transfer for the latter process. In contrast the ferrate(VI) species H3FeO4+ (pKa = 1.6 +/- 0.2), H2FeO4, and HFeO4- oxidize hydrogen peroxide, e.g. k(HFeO4(-) + H2O2) = 170 M-1 s-1), at rates which correspond closely to their dimerization rates suggesting an inner-sphere controlled mechanism.

journal_name

Free Radic Res

journal_title

Free radical research

authors

Rush JD,Zhao Z,Bielski BH

doi

10.3109/10715769609088016

subject

Has Abstract

pub_date

1996-03-01 00:00:00

pages

187-98

issue

3

eissn

1071-5762

issn

1029-2470

journal_volume

24

pub_type

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