A theoretical study
of an electrode mechanism where the
electrode
reaction (E) is preceded by a chemical reaction that takes place solely
at the electrode surface (Chet) is presented under conditions
of square-wave voltammetry (SWV). Rigorous mathematical solutions
in the form of integral equations derived by means of Laplace transforms
are presented for the surface concentration of all species involved
in the electrode mechanism, yielding explicit recurrent formulas for
the simulation of the voltammetric response. The theory approximately
predicts that the chemical reaction starts at the beginning of the
voltammetric experiment, disregarding its occurrence in the short
time period between inserting the electrode in the solution until
starting the voltammetric experiment. It is demonstrated that SWV
can differentiate between the common CE mechanism, where C is a homogeneous
chemical reaction taking place in the vicinity of the electrode, and
the current ChetE mechanism, which is relevant for plethora
of electrocatalytic processes at electrodes modified with catalytically
active enzymes and/or noble-metal nanoparticles, as well as for electrocatalytic
processes of fundamental importance such as CO2, N2, O2, and H+ reductions.