The Characterization of Passivating Films on Commercial Copper Anodes Using Impedance Spectroscopy

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."