Determination of kinetic and thermodynamic parameters from large amplitude Fourier transform ac voltammetry of immobilized electroactive species.

In the present work, the derivation of the standard rate constant k 0, the transfer coefficient a and the standard (or formal) potential E 0 of immobilized electroactive species, with the use of large amplitude Fourier transform alternating current cyclic voltammetry (FTacV) is examined. Both the kinetic equation of the coverage and the current integral equation are solved. The kinetic regions of the current response are distinguished, the chief observables in the case of both fast and slow kinetics are showcased and finally based on these, a methodology to extract k 0, a and E 0 is introduced. • The effect of the kinetic parameters on chief observables is determined. • Chief observables for reversible and irreversible kinetics are examined. • Methodologies to extract kinetic and thermodynamic parameters are introduced. [ABSTRACT FROM AUTHOR]