Chronoamperometry of surface confined redox couples for irreversible two-step and three-step consecutive reaction mechanisms

Chronoamperometry has been widely employed to determine kinetic rate consta nts for electron-transfer reactions of surface-confirmed redox couples. Whe n the mechanism for the transformation is more complicated than a one-elect ron transfer, deviations can be expected from an exponential decay of the c urrent transient. Theory is presented in this paper for irreversible, two-s tep and three-step consecutive reaction mechanisms in the form of analytica l solutions of the corresponding differential equations. The theory should find application to surface electrode reactions with two-electron "n-values ".