Current oscillations during the electrochemical oxidation of sulfide in the presence of an external resistor

Abstract

The electrochemical oxidation of sulfide on a polycrystalline platinum electrode was studied under potentiostatic condition when an external resistor is in series with the working electrode. Only two oscillatory regions can be obtained in the absence of the external resistance, but four oscillatory regions, including two new current oscillations, were found in this system by controlling the external resistance. It is demonstrated that three oscillatory regimes, which arise on the positive branch of current-potential curve, can be classified as HN-NDR (Hidden N-shaped Negative Differential Resistance) oscillators. For the first oscillatory region, various transient complex phenomena, which result from the change of the electrode/electrolyte interface by accumulation of adsorbed element sulfur on the electrode, have been observed. The dynamic behavior of NDR (Negative Differential Resistance) oscillations, appearing along with negative branch of polarization curve, can transform from oscillations into bistability with a sufficient large external resistance in series. Two oscillatory regions in high-potential region classified as HN-NDR type oscillations are separated by a saddle-loop bifurcation. They displayed a sequence of bursting oscillations and irregular oscillations, respectively. The electrochemical oxidation of sulfide provides a model system for studying complex dynamics and possible application in sulfur removal.