The Kinetics of the Copper-Catalysed Oxidation of Thiosulfate in Ammoniacal Solutions

The kinetics of the oxidation of thiosulfate by copper(I I) in ammoniacal solutions have been studied in the presence and absence of dissolved oxygen. The formation of an intermediate mixed ammine/thiosulfate copper(II) complex ion has been confirmed and the rate of the reaction monitored by simultaneous on-line spectrophotometric, dissolved oxygen and potentiometric measurements. The rate of the anaerobic oxidation of thiosulfate by copper(II) was found to be orders of magnitude slower than that in the presence of dissolved oxygen and is inhibited in the presence of ammonia and anions such as sulfate and chloride as a result of competition with thiosulfate for the axial coordination sites on the copper(II) tetrammine complex. In the presence of dissolved oxygen, it was found that the copper(I) thiosulfate complexes are only very slowly oxidized while the copper(I) diammine complex is rapidly reoxidised to the copper(II) state. Thus, the initial rapid reaction with copper(II) leads to a pseudo steady-state condition in which the concentration of copper(I) is relatively constant and the rate of oxidation of thiosulfate can be predicted from the measured rate of oxidation of copper(I) by oxygen in ammoniacal solutions. The effects of the concentrations of ammonia and thiosulfate on the oxidation rate can be rationalized on the basis of the above coupled to the species distribution of copper(I) in the ammonia/thiosulfate system. It is shown that, with relatively simple measurements of dissolved oxygen and copper concentrations, the rate of oxidation of thiosulfate can be predicted under typical leaching conditions.