Determination of the standard rate constant for soluble-soluble quasi-reversible electrochemical systems by linear sweep voltammetry: Application to the electrochemical oxidation on screen-printed graphite electrodes

Semi-analytical approach was used for modeling and establishing Linear Sweep Voltammetry (LSV) profiles in the case of quasi-reversible electrochemical reactions involving soluble species. The effects of charge transfer coefficient (alpha) and dimensionless kinetic rate constant (?) on the shape and position of voltammograms were investigated. The combined effect on the LSV responses, peak current, half peak width and peak potential was also analyzed qualitatively and quantitatively. Kinetic curves were constructed in the form of the change in the LSV characteristics as a function of (alpha, ?) and then modeled by the interpolation functions. The obtained equations are an easy-to-use tool in order to calculate the heterogeneous kinetic rate constant for quasi-reversible charge transfer. Experimental-theory validation has been performed on ferrocyanide oxidation on screen-printed graphite electrodes.

Automated summary

A semi-analytical approach was used to model and establish the profiles of Linear Sweep Voltammetry (LSV) for quasi-reversible electrochemical reactions involving soluble species. The effects of charge transfer coefficient (alpha) and dimensionless kinetic rate constant (?) on the shape and position of voltammograms were investigated. The combined effect on various LSV characteristics, such as peak current, half peak width, and peak potential, were qualitatively and quantitatively analyzed. Kinetic curves were constructed based on the changes in LSV characteristics with (alpha, ?) and modeled using interpolation functions. The obtained equations serve as a user-friendly tool for calculating the heterogeneous kinetic rate constant for quasi-reversible charge transfer. Experimental-theory validation was performed on ferrocyanide oxidation on screen-printed graphite electrodes.