The concentration overpotential of an electrode reaction at a given electrode current density() is basically the difference in equilibrium potentials across the diffusion layer. More precisely, it is the potential of a reference electrode (of the same electrode reaction as the working electrode ) with the interfacial concentrations which establish themselves at , relative to the potential of a similar reference electrode with the concentrations of the bulk solution. From such a measured potential difference,
with flowing, one needs to subtract the ohmic potential drop prevailing between the two
electrodes.
Source:
PAC, 1981, 53, 1827
(Nomenclature for transport phenomena in electrolytic systems)
on page 1838