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Square-wave voltammetry of quasi-reversible electrode processes with coupled homogeneous chemical reactions

The electrochemical behaviour of systems complicated by electrode kinetic and quasi-reversible preceding or following homogeneous chemical reactions under square-wave voltammetry (SWV) conditions is analysed theoretically. The esults are discussed in detail, considering the influence of rate and equilibrium constants, together with experimentally controlled parameters such as f ad Esw. Both kinetic stages act synergistically for the case of CE mechanism, but EC reaction scheme exhibits more complex behaviour, especially for reversible and quasi-reversible electrochemical reactions, which present a minimum response of current for the quasi-reversible chemical reactions. These curves are characteristical for each system, providing not only the bases for their distincion but also for the kinetic and thermodynamic information.

square-wave voltammetry; simulation; coupled chemical reactions; mechanistic studies; mathematical models

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