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279 Friedrich, B., Z. Havlas, Z. Herman, and R. Zahradnik, Theoretical studies of reaction mechanisms in chemistry, Advances in Quantum Chemistry, Vol. 19 (Ed. P. O. Lovdin), Academic Press, Orlando, 1987. Koryta, J., see page 191. Koryta, J., Ion transfer across water/organic solvent phase boundaries and analytical applications, Part 1, 2, Selective El. Revs., 5, 131 (1983), 13, 133 (1991). Levich, V. G., Kinetics of reactions with charge transport, PChAT, IX B, 985 (1970). Marcus, R. A., Chemical and electrochemical electron-transfer theory, Ann. Rev. Phys. Chem., 15, 155 (1964). Marcus, R. A., Electron, proton and related transfers, Faraday Discuss. Chem. Soc, 74, 7 (1982). Marcus, R. A., and N. Sutin, Electron transfers in chemistry and biology, Biochim. Biophys. Acta, 811, 265 (1985). Marecek, V., Z. Samec, and J. Koryta, see page 243. Newton, M. A., and N. Sutin, Electron transfer reactions in condensed phases, Ann. Rev. Phys. Chem., 35, 437 (1984). Tsonskii, V. S., L. B. Korsunov, and L. I. Krishtalik, Electrochim. Acta, 36, 411 (1991). Vanysek, P., see page 191. 5.4 5.4.1 Transport in Electrode Processes Material flux and the rate of electrode processes



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Material changes occurring during electrolysis at electrodes lead to mass transport throughout the whole system. The mathematical treatment of electrode processes involves relationships between the concentrations, their gradients and the current densities, corresponding to the rates of processes occurring directly at the electrodes (primarily the rates of electrode reactions), as boundary conditions for the differential equation describing transport processes in the electrolyte, formulated in 2. Sometimes (small currents, strong mixing), the concentration changes are so small that the effect of transport phenomena can be neglected. According to Faraday's law, the current passing through the electrode is equivalent to the material flux of electroactive substances. The disappearance of electroactive substances in the electrode reaction is considered as their transport through the electrode surface. Consequently, only diffusion and migration but not convection flux need be considered at the electrode surface, as the electrode is impenetrable to the solution components. Assume that both the initial substances and the products of the electrode reaction are soluble either in the solution or in the electrode. The system will be restricted to two substances whose electrode reaction is described by Eq. (5.2.1). The solution will contain a sufficient concentration of indifferent electrolyte so that migration can be neglected. The surface of the electrode is identified with the reference plane, defined in Section 2.5.1. In this plane a definite amount of the oxidized component, corresponding to the material flux /Ox and equivalent to the current density /, is formed or

280 disappears in unit time. The reduced form participates in the reverse process, connected with the material flux / Red . When both forms are present in solution j = nFJOx = -nFJRcd j=-nFDOx[ -\

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