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Abstract: Cyclic voltammetry is widely used to investigate redox systems and is especially useful for determining electrode kinetic data. Experiments to obtain this data typically involve measuring the peak-to-peak separation as a function of voltage scan rate and applying appropriate theory. Experimental data are almost invariably measured using a digital potentiostat and as such the applied potential will have been varied in a series of discrete steps separated by a value . In this work, we calculate the error introduced by approximating a potential ramp as a staircase and consider how this insight may be used to ensure that electrode kinetic parameters extracted from experimental voltammetry so measured are accurate. [Copyright &y& Elsevier]

Abstract: The size of microdroplets of dodecane of approximately 5μm diameter immobilised on a regular array of hydrophobic polymer blocks of a partially blocked electrode is determined by comparison of a simple electrochemical procedure with simulations. The electrochemical procedure is based on a simple Cottrellian-like potential-step experiment, where the current response is monitored as a function of time. Excellent agreement is found between theory and experiment thus giving physical support for the expected transition in diffusion layer shape and size. [Copyright &y& Elsevier]