| Abstract: | Allowing for the interfacial potential distribution it can be shown that the apparent faradaic electron number, n app, of ad-layers of chemically modified electrodes and the surface redox valency, n , relating to the slope of the peak potential/pH response [Huck (2002) J Solid State Electrochem 6:534] are at least identical, having the same thermodynamic origin. napp is calculated from the cyclovoltammetric (CV) peak areas above the interpolated base line. At  for proton-coupled surface redox reactions, the influence of the potential drop of the diffuse double layer disappears because the capacitor of the corresponding equivalent circuit becomes shortened by proton transfer, whereby the otherwise non-integer napp or n values now approach the integer electron numbers, n, of the Nernst equation. |
