Theoretical and experimental square wave voltammetry

The theory of square wave voltammetry was extended to include electron transfer kinetics, and first order preceding, following and catalytic reactions. The effects of these complications upon experimentally measurable peak positions, heights and widths were predicted by the numerical solution of the integral equations describing the systems. A fast scan square wave technique useful at frequencies up to 1250 Hz and scan rates of 6.25 volts per second was developed to test the theoretical predictions experimentally. A laboratory minicomputer interfaced to a static mercury drop electrode was used for data acquisition and real time control of the experiment. The quasireversible reduction of zinc, the dissociation of cadmium EDTA preceding electron transfer, the rearrangement of hydrazobenzene following electron transfer, and the catalytic reduction of titanium were chosen as model systems.