Normal Pulse Voltammetry and Steady State Voltammetry of the Square Mechanism at Spherical Microelectrodes

Abstract A simple analytical solution is presented for the study of the square mechanism in normal pulse and steady state voltammetries at spherical (ultra)microelectrodes. The analytical expression deduced enables the description of a broad range of situations depending on the chemical kinetics and the difference between the half‐wave potentials of the electron transfers. Regarding the chemical kinetics, the electrochemical response is analysed from the limit of slow kinetics, where the thickness of the reaction layer tends to coincide with that of the diffusion layer, up to the limit of very fast kinetics, where the reaction layer vanishes. Finally, the conditions under which the total steady state response is sensitive to the homogeneous kinetics are studied.