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. (C) 2014 Elsevier B.V. All rights reserved.