Theory of square-wave voltammetry for the analysis of a CE reaction mechanism complicated by the adsorption of the reactant

VETTORELO, SABRINA N.; CUÉLLAR, MARIELA; ORTIZ, PATRICIA I.; GARAY, FERNANDO

JOURNAL OF ELECTROANALYTICAL CHEMISTRY - (Print)

ELSEVIER SCIENCE SA

Año: 2019 vol. 852

1572-6657

his manuscript presents a theoretical work about an electrode process preceded by a chemical reaction involving adsorbed species, where both reactions canpresent any degree of reversibility. The electrode reaction involves an adsorbed reactant that releases the product in solution, which is a reaction mechanism that is typically found for the cathodic stripping voltammetric response of metal complexes. To the best of our knowledge this the first time that a general mathematical solution that merges the effects of diffusion, adsorption and other parameters associated with the kinetics and thermodynamics of this reaction mechanism is presented. The analysis is focused on the description of square-wave (SW) voltammetric profiles where the preceding chemical reaction involves a partially labile complex. It is important to point out that the value of frequency at the so-called ?quasi-reversible maximum? is not shifted due to a quasi-labile preceding chemical reaction, and that typical expe