Simulation of square-wave voltammetry: EC and ECE electrode processes

A simulation of square-wave voltammetry (SWV), based on the backward implicit method, is developed to encompass EC and ECE mechanistic schemes. The processes considered are assumed to be electrochemically reversible, and the voltammetric properties-peak current, peak voltage, and half-height width-are shown to give good agreement with approximate analytical solutions, where available. The simulations are computationally efficient and facilitate the construction of informative concentration profiles for all reacting species. Further, the inclusion of diffusional effects based on convective control of the diffusion layer thickness is shown to be possible, thereby permitting the quantitative use of SWV for mechanistic studies at hydrodynamic electrodes. © 2000 American Chemical Society