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- W1515422807 abstract "Orthogonal collocation was used to obtain an efficient iterative solution to the problem of the second-order EC-catalytic mechanism at the rotating disk electrode (RDE). Application of the spline collocation technique provided accurate results for large values of the kinetic parameter or the substrate/catalyst concentration ratio. The numerical solution was in good agreement with approximate analytical solutions available for certain limiting cases. The second-order EC-catalytic mechanism at the RDE was used to measure the rate of reaction between bipyridinium cation radicals and dioxygen in non-aqueous solutions. Sixteen diquaternized derivatives of 2,2′- and 4,4′-bipyridine were studied including the commercially available herbicides diquot and paraquat (methyl viologen). Values obtained for the rate constant k1 in acetonitrile ranged from 5 × 103 M−1 s−1 to 2 × 108 M−1 s−1. The dependence of log k1 on the standard potentials of the reactants conformed to the Marcus equation for an activation-controlled reaction. The result obtained for the Gibbs energy of activation, 13.1 kJ/mol, was in good agreement with that calculated using the standard rate constant for the heterogeneous reduction of dioxygen. The rate constants in acetonitrile also showed a strong correlation with published data on the herbicidal activity of selected bipyridinium compounds in mustard and tomato." @default.
- W1515422807 created "2016-06-24" @default.
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- W1515422807 date "1990-11-01" @default.
- W1515422807 modified "2023-10-10" @default.
- W1515422807 title "The EC-catalytic mechanism at the rotating disk electrode" @default.
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- W1515422807 doi "https://doi.org/10.1016/0022-0728(90)87132-4" @default.
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