https://doi.org/10.1351/goldbook.C01230
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.