Abstract
The effect of varying the applied potential during progressive three-dimensional nucleation and growth is described. The assumed model is that due to Armstrong, Fleischmann, and Thirsk in which expanding nuclei are considered to be right circular cones distributed at random on the electrode surface. The present work extends the previous potentiostatic approach by considering that the electrode surface coverage function responds instantaneously to small changes of applied potential. Under these circumstances we show that it is possible to calculate in an exact way the theoretical response of the model to various applied potential waveforms. In particular, the linear potential sweep and the staircase potential ramp are considered, as well as feedback loops generated by uncompensated ohmic overpotential. Certain limiting cases are derived which may be tested by experiment.
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