ANOMALIES OF STAIRCASE VOLTAMMETRIC PEAKS OBTAINED FOR THE REDUCTION OF METAL-IONS IN THE ABSENCE OF SUPPORTING ELECTROLYTE

Staircase voltammetric (SCV) peaks for the reduction of metal cations obtained in the absence of supporting electrolyte are much less sensit ive to the current-sampling parameter cu compared with processes havin g purely diffusional transport and excess supporting electrolyte. This is apparently connected with the existence of an increased and changi ng in time uncompensated resistance. To obtain SCV peaks of identical height to the linear scan peaks, alpha should be set to 50% or the cur rent should be measured at one half of the pulse time. It has also bee n demonstrated that, at an intermediate level of supporting electrolyt e, the staircase waveform apparently generates convectional transport at the surface of a hanging mercury drop electrode.