Fourier Transformed AC Voltammetry (FTACV) commonly employs a single frequency sinusoidal waveform superimposed onto a DC ramped potential. If the amplitude is large enough, non-linearity in the faradaic electron transfer response leads to detection of the aperiodic DC, fundamental harmonic, second harmonic and a series of higher order harmonics. The features of the faradaic response are governed by the thermodynamics in combination with the kinetics of the electron transfer process and coupled chemistry, with the higher order AC components being particularly sensitive to the electrode kinetics. Importantly, the second harmonic ideally, but third and higher in practice, are devoid of background current arising from double layer capacitance charging or other processes. Many variations of FTACV are also available. For example, a single sinewave with no DC ramp or instead of a single sine wave, two, three or multiple sinewaves can be superimposed onto the DC ramp, or a square wave can be employed. Electrochemical Impedance Spectroscopy (EIS) represents one limit of applying multiple sine waves, traditionally at a fixed DC potential but now more commonly also onto a ramped DC potential. Thus, it can now be recognised there is large family of AC methods are available that are all governed by closely related instrumental and theoretical principles. In the first part of this lecture, data analysis by FTACV for the well-known Fc0/+ process(Fc = Ferrocene) will be extended to the rarely studied Fc+/2+ reaction which is an Fe(III) to Fe(IV) reaction accessible at very positive potentials in ionic liquids at glassy carbon and boron doped diamond electrodes. Novel features relevant to the Fc0/+/2+ reaction sequence, anomalous background current, ionic liquid voltammetry, and carbon electrodes at very positive potentials emerge from analysis of single sine wave FTACV based on comparisons of simulated responses and experimental data, use of multiparameter fitting by data optimisation and Bayesian inference. The lecture will then conclude by considering the implications of using an analogous approach to analyse data obtained by application of multiple sine waves rather than a single sine wave and the relationship to data analysis as in EIS where equivalent circuit analysis has been employed instead of models based on thermodynamics combined with electrode and chemical kinetics.
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