Calculating of square-wave voltammograms—a practical on-line simulation platform

Abstract

Square-wave voltammetry (SWV) is a widely used technique for getting insight into mechanistic and kinetic aspects of various electrochemical reactions. To date, this pulse-voltammetric technique has been utilized in numerous electrochemical studies and it remains one of the most sophisticated electrochemical methods available. As a result of its higher sensitivity and its potential to provide insights similar to cyclic voltammetry for electrode mechanisms characterization, the SWV is increasingly being included in undergraduate electrochemistry laboratory curriculums. The features of experimental SW voltammograms are affected by various factors, such as kinetics of charge transfer, diffusion, adsorption phenomena, and chemical reactions coupled to electron transfer step. To understand some of the physical and chemical phenomena hidden in a single experimental SW voltammogram, it is inevitable to get a help of computer simulations. The purpose of this article is to offer a basic introduction to SWV written in a simple language, intended to engage students and familiarize them with the fundamentals of this technique. The ultimate objective is to provide the aspiring young electrochemists with a simulation procedure using the MATHCAD software, which can be employed to compute SW voltammograms following a rather easy simulation approach. A detailed tutorial on simulating SW voltammograms with MATHCAD software is presented. The simple tutorial offers a step-by-step breakdown of the simulation process of a square-wave voltammogram. Additionally, a MATHCAD ready-to-use file for simulation of a common electrode mechanism is provided. The current work aims to assist undergraduate students in learning about electrochemical simulations that serve as a corner stone to more advanced studies in SWV.