Calculations of the H/D and H/T separation factors (S) and exchange current density ratios (R) for the proton discharge mechanism on mercury, nickel, and iron are presented. A vibrational analysis of the activated complexes is made by reference to both a linear three‐center transition state model and a surface interstitial site model in which H is regarded as being adsorbed adjacent to two metal atoms in the surface. It is shown that the isotope effects observed experimentally, e.g. at mercury, can be accounted for in terms of a slow proton discharge mechanism. Calculations are made for discharge from H3O+ and H2O molecules. The values of R are shown to be consistent with the values of SD calculated and observed. An explanation is also given qualitatively for the potential dependence of SD at mercury in terms of electrostriction effects in the double layer.