ABSTRACT Theoretical and experimental results are presented for the response corresponding to a simple charge transfer reaction when potential-controlled voltammetry at constant sphericity is applied to mercury electrodes, i.e. a stationary spherical electrode such us the static mercury drop electrode (SMDE) and also a dynamic one, the dropping mercury electrode (DME). The use of constant sphericity at these electrodes lends great advantages since it allows us, on the one hand, to discriminate between kinetic and curvature effects, and, on the other, to reduce the undesirable effects from uncompensated IR drop. In addition, we show for the DME that convective effects can be controlled experimentally and some disadvantages of this electrode can be obviated. Methods for determinating heterogeneous kinetic parameters are also discussed.
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