Electrochemical modeling and study of copper deposition from concentrated ammoniacal sulfate solutions

A fundamental investigation of the electrolytic deposition of copper from concentrated aqueous ammoniacal solutions has been carried out based on the thermodynamic analysis of the system Cu–NH3–H2O. The speciation of copper vs. pH and redox potential was modeled in high ionic strength solutions, in which the activity coefficients of the system species were estimated according to the Modified Bromley's Methodology. The electrochemical behavior of the redox system Cu(0)/Cu(I)/Cu(II) in concentrated aqueous ammoniacal solutions was studied at pH = 9.5 and the cathodic reactions in these solutions were determined. It was found that metallic copper was formed under strongly reductive redox conditions, while under mildly reductive to mildly oxidative conditions the cuprous di-ammine complex species dominate. Under highly oxidative conditions the cupric tetra-ammine complex species predominated. According to the theory and results, the cathodic deposition of copper from concentrated aqueous ammoniacal solutions proceeds in a two-step reduction mechanism. The cupric ammine species are first reduced to cuprous di-ammine, which in turn is reduced to metallic copper. The electrochemical experiments revealed that copper deposition over time follows a sigmoid-type curve, verifying the two-step mechanism. The main feature of these sigmoid curves was the presence of an induction period with negligible copper deposition, followed by an acceleration period where the copper deposition rate gradually increased. By increasing the applied cell voltage, the induction period was significantly reduced or disappeared.