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• W2090830650 abstract "The overall charge-transfer reaction at [Ru(NH3)6]3+/2+-containing montmorillonite clay film-coated graphite electrodes was examined quantitatively by cyclic voltammetry, potential-step chronoamperometry (chronocoulometry) and normal pulse voltammetry. The relevant kinetic parameters (i.e. the standard rate constant k°/cm s−1 and the cathodic transfer coefficient αc) of the heterogeneous electron-transfer reaction of the [Ru(NH3)6]3+/2+ couple at the electrode/film interface and the apparent diffusion coefficient (Dapp/cm2 s−1) of the homogeneous charge-transport reaction within the film were evaluated at various concentrations (c° = 1 mol dm−3) of the complex within the films. It was found that Dapp, k° and αc change significantly with c° in the range of c° from 0.04 to 0.4 M; they increase with increasing c° in the lower c° range, reach their maximum values, and then decrease with increasing c° in the higher c° range. These kinetic parameters were also found to depend in different ways on the solution pH (pH 1–10). Under the condition of constant c°, no influence of the supporting electrolytes (Na2SO4, NaCl, NaBr, CH3COONa, CF3COONa, p-CH3C6H4SO3Na) on k°, αc and Dapp was observed. From the temperature dependences of the formal redox potential (E°') and Dapp, the reaction entropy (ΔS°rc) of the [Ru(NH3)6]3+/2+ couple within the clay film and the activation parameters of the homogeneous charge-transport reaction were evaluated. The mechanism of the charge-transport process within the clay film and the effects of the polymer domain, pH and supporting electrolyte on the rates of the heterogeneous electron-transfer and homogeneous charge-transport processes are discussed on the basis of an electron-hopping reaction, physical diffusion of [Ru(NH3)6]3+ (and [Ru(NH3)6]2+) and electrolyte ions, electrostatic cross-linking, single-file diffusion, structures of clay, electrode surface charge, etc." @default.
• W2090830650 created "2016-06-24" @default.
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• W2090830650 date "1991-10-01" @default.
• W2090830650 modified "2023-09-25" @default.
• W2090830650 title "Electrode kinetics of [Ru(NH3)6]3+/2+complex confined in montmorillonite clay coatings on graphite electrodes" @default.
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• W2090830650 doi "https://doi.org/10.1016/0022-0728(91)80068-2" @default.
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