Models for the Diffusion Coefficient of Cupric Ion and Limiting Current Density in a Copper Electrorefining Electrolyte

"The diffusion rate of cupric ions and limiting current density are important factors that determine the rate of copper mass transport in electrolytes proximal to the electrodes used in electrorefining. As a result, diffusion can critically affect both the rate and morphology of cathodic copper deposition thus it is crucial that it be optimized to improve production. The diffusion coefficient of cupric ion (DCu(II)) in copper electrolytes has been previously researched but the values detailed in the literature show significant variations and moreover arsenic - a common impurity - is generally excluded. Furthermore, in previous studies the models have only been validated with model solutions rather than real industrial electrolytes. In this study, the limiting current density and diffusion coefficient of cupric ion were defined for synthetic electrolytes containing copper (40–60 g/dm3), nickel (0–20 g/dm3), sulfuric acid (130–220 g/dm3) and arsenic (0–45 g/dm3). The cathodic limiting current densities were measured at three temperatures (50, 60, 70 °C) with linear sweep voltammetry using the rotating disc electrode (RDE) as the cathode. By utilizing the limiting current density, models for the DCu(II) were constructed using Levich equation. The validity of the DCu(II) model for technical use was confirmed through their application to industrial electrorefining electrolytes with known element concentrations. Consequently, this study provides improved models for limiting current density and diffusion coefficient of cupric ion that can be utilized for industrial process optimization.INTRODUCTION For an efficient copper electrolysis process, the mass transport of copper ions has to be effective. The main mass transport types of copper ions in copper electrorefining are diffusion and convection while the effect of migration is negligible. In order to maintain good mass transport, it is beneficial to keep both diffusion and convection high to maximize the limiting current density (jlim) (Bard and Faulkner, 2001). jlim is the highest current density that can flow in the cell, thus by maximizing jlim the deposition time can be minimized and the good quality of cathodic copper can be ensured. Thus, it is important to research possibilities that increase and optimize diffusion since slow diffusion in the electrolyte limits the rate of the process (Levich, 1947; Moats et al., 2000; Subbaiah and Das, 1989)."