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By Abello T.P.

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This is correct for the interaction due to electric polarization which is important in polar solvents. It is not such a good approximation for vibrational interactions where the force constants can change considerably for different states of oxidation. Nevertheless, neglecting such complications is helpful for the basic understanding. 75) Assuming a parabolic relation of the same shape for Gox(ρ) and Gred(ρ) around their minima, one can describe the parabola by Copyright © 1997 by CRC Press, Inc.

It remains therefore at its equilibrium potential. As for all interfacial reactions, transport of the reactants to the interface from the bulk and, vice versa, removal of the products from the interface, are inherent steps in the overall Copyright © 1997 by CRC Press, Inc. 17. Electron transfer between a metal electrode and a redox couple in solution via tunneling through the energy barrier at the interface. kinetics of electrode reactions. If the charge transfer step at the interface is fast, the transport processes become rate controlling very shortly after the start of the reaction.

18,22 They can accumulate additional charge on the surface which affects the potential drop in the Helmholtz layer. Copyright © 1997 by CRC Press, Inc. 16. Mott–Schottky plots for a CdS electrode in two different electrolytes and determination of the flatband potential Ufb. Because this charge varies with the applied voltage, deviations from the linearity of the Mott–Schottky plot result, particularly when one approaches the flatband potential. Similar consequences arise from donor or acceptor states with energies deeper in the band gap which are not ionized at the flatband potential, but become charged at a larger potential drop in the depletion layer.

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