Comparison of fundamental and second-harmonic a.c., and normal, derivative and differential pulse linear-sweep and stripping voltammetric methods

Abstract

Linear-sweep and stripping a.c. and pulse voltammetric methods have been compared for a variety of electrodes and electrode processes. Each of the linear-sweep techniques is readily used systematically because, in contrast to d.c. linear-sweep voltammetry, the theory for reversible electrode processes is basically analogous to that for polarography at a dropping mercury electrode. In stripping analysis, some departures are found at a hanging mercury drop electrode because of spherical diffusion effects. For reversible electrode processes, the limits of detection for a.c. and pulse methods are comparable. However, a.c. methods offer advantages over pulse methods in discriminating against irreversible electrode processes and permit the ready use of faster scan rates. Pulse methods are more sensitive for irreversible electrode process. Normal pulse polarography is particularly favourable in minimizing undesirable phenomena arising from adsorption or deposition of material on electrodes.