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1 Polish Journal of Chemistry

1 2004

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Oxidation of Hexacyanoferrate(II) by Peroxynitrite. A Mechanistic and Kinetic Study

Martinez E., Mucientes A., Poblete F., Rodriguez A.

Polish Journal of Chemistry

2004

Vol. 78 / nr 2

261-271

Akinetic study of the oxidation of hexacyanoferrate(II) by peroxynitrite has been carried out, using a stopped-flow technique. The variation of the experimental rate constant over a wide concentration range of Fe(CN)6 4 has been investigated under different experimental conditions in terms of pH, ionic strength and temperature. Acorrelation between kexp and the substrate concentration has been obtained and this shows first-order behavior in substrate at high concentrations of Fe(CN)6 4 .Areaction mechanism is proposed, in which the hexacyanoferrate(II) reacts in competitive pathways with the peroxynitrous acid (direct oxidation) and with HOź and źNO2 radicals formed in the homolysis of the peroxide bond ofHOONO(indirect oxidation). Moreover, two individual constants, kc (the formation constant of the germinated radical pair [HOź źNO2]) and k7 (direct oxidation constant), have been evaluated together with the thermodynamic parameters of these elementary steps.