Second harmonic ac polarography of strongly adsorbed electroactive species

Abstract The second harmonic ac current is calculated for the case of a quasi-reversible surface redox system: both species are strongly adsorbed according to a Langmuir isotherm and the kinetics of the process are controlled by the electron transfer. The current is measured with a phase-sensitive detector and the variation of the in-phase and quadrature components vs. the frequency leads to the surface rate constant ks. The experimental results obtained for benzo-(c)cinnoline are in good agreement with the theoretical predictions and with the results of impedance measurements. The advantages of the two methods are compared.