The numerical integration of the differential equation for cyclic voltammetry has been performed for the case where the reverse potential is set prior to the forward peak potential. A working curve stemming from these integrations allows the determination of the half-wave potential of species limiting the potential window. This technique has been applied to the measurement of formal Gibbs energies of transfer of ions across the water/ 1,2-dichIoroethane interface. The validity of the TATB (tetraphenylarsonium tetraphenylborate) assumption is also discussed.
A theory for cyclic voltammetry at liquid/liquid interfaces for electron transfer is proposed, and the numerical solution of the resulting integral equation is evaluated. This theory has been used to show how the cyclic voltammograms, for electron transfer at ITIES, vary when different ratios of reactants and products, in both phases, are used, and how these voltammograms differ from classical cyclic voltammograms.
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