Current‐Potential‐Time Response of the Second‐Order Co‐Reactant Mechanism: An Analytical Theoretical Approach

Abstract An analytical approach is presented for the voltammetric and chronoamperometric study of a second‐order cyclic‐type mechanism where two species are ‘activated’ electrochemically and subsequently react in solution, as observed in co‐reactant electrochemiluminescence mechanisms. Closed‐form expressions are derived for the current‐potential‐time response and for the surface species concentrations as a function of the chemical rate constant, the concentration ratio of the initial species, and their formal potentials. Their effects on the voltammetric signal are analyzed, pointing out a wave‐splitting behaviour for fast kinetics, which is tied to the rates of formation and consumption of the ‘activated’ co‐reactant.