Demystifying Mathematical Modeling of Electrochemical Systems

One of the unique advantages of electrochemistry is that the relationship between thermodynamics and kinetics is quantitative, which is the basis of voltammetry. Mathematical models of electrochemical systems take advantage of this relationship to predict the effect of changing a system property (e.g., concentration, scan rate, or rate constant) with high accuracy. This insight enhances understanding of the link between experimental settings and their resulting effects and further allows optimal values to be determined before the experiment begins. This work introduces the electrochemical theory and process of building one of these models for an example system of ferricyanide undergoing reduction during a linear sweep voltammogram, a common experiment in undergraduate laboratories. A MATLAB code for finite difference implementation of this model is provided, as well as a list of suggested exercises for modifying or extending this code, which could be used a problem set in undergraduate or graduate course work.