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Issue 19, 1992
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Non-linear arrhenius behaviour of the rate constants of some activation-controlled reactions of the hydrated electron in the temperature range 20–200 °C

Abstract

Rate constants for the reaction of eaq with N2O, NO3, NO2, phenol, SeO2–4, S2O2–3 and Mn2+ have been measured in the temperature range 20–200 °C by pulse radiolysis. In each case non-linear Arrhenius behaviour of the rate constant has been observed for the activation-controlled part of the overall process of diffusion and reaction. The activation energies (E)a decrease with increasing temperature and, except for Mn2+, become negative. The data are interpreted in terms of a model for reversible electron transfer which implies that activation-controlled reactions of eaq may be reversible. In the case of Mn2+, Ea first decreases and then increases with increasing temperature. It is suggested that a second channel becomes operative at elevated temperatures for the reaction of eaq with Mn2+.

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Article type: Paper
DOI: 10.1039/FT9928802833
Citation: J. Chem. Soc., Faraday Trans., 1992,88, 2833-2836
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    Non-linear arrhenius behaviour of the rate constants of some activation-controlled reactions of the hydrated electron in the temperature range 20–200 °C

    G. V. Buxton and S. R. Mackenzie, J. Chem. Soc., Faraday Trans., 1992, 88, 2833
    DOI: 10.1039/FT9928802833

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