A new modeling method for determining electrochemical parameters from LSV experiments using the stochastic noise. Part II: Experimental validation

• The new modeling procedure for electrochemical kinetics is experimentally validated.
• It is applied to individual polarization curves for parameter estimation.
• Two one electron transfer (reversible and irreversible) reactions are modeled.
• The results for single experiments are compared to those for the set of curves.
• The influence of the experimental error on the parameter estimation is shown.

A novel modeling procedure to accurately determine the characteristic parameters of an electrochemical reaction from polarization curves, presented in the first part of this series, is validated now on voltammetry experiments. The combination of the local polynomial model and the analytical fitting allows determining the electrochemical parameters (rate constants, charge transfer coefficients, etc.) from one polarization curve. Linear sweep voltammetry coupled with rotating disk electrode is used to study two one-electron transfer reactions: the ferri/ferrocyanide reaction and the electroreduction of hexaamminecobalt(III). This approach enables the assessment of the quality of the modeling and the analysis of the influence of the experimental variations on the calculated parameters.