A theoretical analysis of fast Fourier transform methods in hydrodynamic modulation voltammetry (HMV) is presented for the determination of frequency response spectra. The speed of a rotating disk electrode is modulated in a manner that simultaneously excites many frequencies so that Fourier decomposition of the mass‐transfer limited current output signal gives the system response (amplitude and phase) over the entire frequency spectrum. Nonlinear harmonic interactions that can give rise to significant deviations from linear system response are discussed in detail. Existing linear theories are compared with the numerical results, and upper bounds are established for the modulation amplitudes that give linear response in HMV systems. Results are presented for large amplitude sinusoidal, square root, and triangular modulations in the speed of a rotating disk electrode.
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Schwartz et al. (1989) studied this question.
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