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Iron(II) sulfate oxidation with oxygen on a Pt/C catalyst: A kinetic study

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Abstract

The kinetics of iron(II) sulfate oxidation with molecular oxygen on the 2% Pt/Sibunit catalyst was studied by a volumetric method at atmospheric pressure, T = 303 K, pH 0.33–2.4, [FeSO4] = 0.06−0.48 mol/l, and [Fe2(SO4)3] = 0−0.36 mol/l in the absence of diffusion limitations. Relationships were established between the reaction rate and the concentrations of Fe2+, Fe3+, H+, and Cl− ions in the reaction solution. The kinetic isotope effect caused by the replacement of H2O with D2O and of H+ with D+ was measured. The dependence of Fe2+ and Fe3+ adsorption on the catalyst pretreatment conditions was studied. A reaction scheme is suggested, which includes oxygen adsorption, the formation of a Fe(II) complex with surface oxygen, and the one-electron reduction of oxygen. The last step can proceed via two pathways, namely, electron transfer with H+ addition and hydrogen atom transfer from the coordination sphere of the iron(II) aqua complex. A kinetic equation providing a satisfactory fit to experimental data is set up. Numerical values are determined for the rate constants of the individual steps of the scheme suggested.

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  1. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090, Russia

    L. B. Okhlopkova & N. I. Kuznetsova

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  1. L. B. Okhlopkova
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  2. N. I. Kuznetsova
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Correspondence to L. B. Okhlopkova.

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Original Russian Text © L.B. Okhlopkova, N.I. Kuznetsova, 2008, published in Kinetika i Kataliz, 2008, Vol. 49, No. 1, pp. 39–47.

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Okhlopkova, L.B., Kuznetsova, N.I. Iron(II) sulfate oxidation with oxygen on a Pt/C catalyst: A kinetic study. Kinet Catal 49, 34–42 (2008). https://doi.org/10.1134/S0023158408010059

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