An integrated instrumental and theoretical approach to quantitative electrode kinetic studies based on large amplitude Fourier transformed a.c. voltammetry: A mini review

Herein, we emphasise the main advantages provided by Fourier transform assisted a.c. voltammetry over d.c. methods in quantitative electrode kinetic studies and report on the progress with integration of the a.c. approach with contemporary computer-assisted automated data analysis methods. In the mechanistically sensitive version of Fourier transformed a.c. voltammetry emphasised in this mini review, a large amplitude sinusoidal or another time dependent periodic function is superimposed onto the d.c. potential ramp. Using a sequence of Fourier Transform and filtering operations, both experimental and simulated data for the assumed mechanism are resolved into the aperiodic (d.c.) and a.c. harmonic components. Comparison of experiment and theory by heuristic or computer-assisted automated methods allows quantitative estimates to be provided of the relevant thermodynamic and kinetic parameters as well as of uncompensated resistance, double layer capacitance and other parameters present in the electrode kinetics model. Crown Copyright (C) 2015 Published by Elsevier B.V. All rights reserved.