In this article we establish the necessary mathematical conditions for the superposition principle to be applicable in obtaining the response for different electrochemical techniques on plane, spherical and cylindrical electrodes.

In potential controlled techniques, this principle can be only applied when the electrical transference is reversible. No additional restrictions exists for planar electrodes. When the electrode is spherical or cylindrical, in addition, the reactive and product diffusion coefficients must be equal and the reaction product must be soluble in the solution. When these conditions are fulfilled, the superposition principle can be applied to any sequence of pulses. Moreover, for spherical electrodes this principle can be applied although the amalgamation took place when only the first order spherical correction is considered.

In current controlled techniques this principle can be used independently of the reversibility of the system and the solutions thus obtained are valid for any electrode geometry both in the case of the reaction product being soluble in the solution and in the electrode (amalgam formation).