Analytical I–E response for several multistep potential techniques applied to an electrocatalytic process at mediator modified electrodes

General analytical and explicit equations for the transient and stationary I–E responses of electrocatalytic process of soluble solution species at mediator modified electrodes, valid for any reversibility degree of the charge transfer and for any multipotential pulse technique, are presented. These expressions have been applied to staircase voltammetry (SCV) and linear sweep voltammetry (LSV), and also to their corresponding differential and derivative modalities. The value of the chemical rate constant can be easily obtained from a cathodic plateau of the SCV curves under transient and stationary conditions. Easy methods for determining other characteristic parameters of the process are proposed. The theoretical predictions have been experimentally tested.