Oxidation of hydrosulphide ions on gold Part I: A cyclic voltammetry study

The results of an investigation to determine the mechanism(s) of oxidation of sulphide ions on a gold electrode are discussed. The cyclic voltammetry results are presented in Part I and characterization results after various electrochemical pretreatments are to follow in Part II. The cyclic voltammetry studies show that several stages are involved in oxidation of sulphide ions to form elemental sulphur. Initially, sulphide ions undergo underpotential deposition to form chemisorbed sulphur as isolated atoms. As oxidation proceeds, a monolayer of chemisorbed atoms is formed which reacts with sulphide ions in solution to form polysulphides at higher potentials. As the potential for oxidation is further increased elemental sulphur is produced. The reduction of polysulphide to hydrosulphide ions occurs by a 2-electron transfer process whereas the reduction of elemental sulphur occurs by a l-electron transfer process. The latter reaction involves the formation of an activated complex which is a relatively slow process.