A.C. Cyclic voltammetry: A digital simulation study of the slow scan limit condition for a reversible electrode process

Rate laws presented to date for analysis of a.c. cyclic voltammetric data have invoked the so-called “slow scan limit approximation” which requires that ΔEω ? v, where Δ E and ω are the applied a.c. potential amplitude and angular frequency, respectively, and v is the d.c. potential scan rate. To provide a more useful guideline for the experimentalist than this qualitative condition, a pure digital simulation approach has been used to compute the a.c. cyclic time domain waveform for a reversible process under small amplitude conditions. The a.c. content of this waveform is extracted by the digital FFT alogirthm. Results of this study are presented here. Among the conclusions reached are more quantitative limitations for the slow scan limit rate laws describing the fundamental and second harmonic responses (approximately 128 a.c. cycles/d.c. cyclic sweep and 512 a.c. cycles/d.c. cyclic sweep, respectively) and an interesting prediction that the latter limitations can be relaxed further by a current waveform subtraction strategy, to as low as about 16 a.c. cycles/d.c. cyclic sweep for the fundamental and second harmonics. The cycles/sweep values assume one triangular wave potential scan of ±200 mV is encompassed.