Activation energy of electrochemical reaction at a constant value of electrode potential

Equations were derived interrelating ideal activation energy W (determined at the constant Galvani potential value), real activation energy A (determined at a constant overpotential), and the so called formal activation energy Ω (calculated at a constant electrode potential vs. an arbitrarily chosen reference electrode). The obtained equations include only the parameters of the studied reaction and no characteristics of the reaction occurring on the reference electrode. The type of the Ω dependence on the electrode potential is established. Conditions are found, under which the real and formal activation energies of the electrochemical reactions can simultaneously remain constant in the given temperature range and it becomes possible to use them in the integral forms of the Arrhenius equation.