Copper Solubility and Redox Equilibria in Magnesia Saturated CaO-CuOx-FeOx Slags

Abstract

New measurements on solubility of copper and redox equilibria in magnesia-saturated calcium ferrite-based slags are presented. These data were obtained from equilibrium experiments at 1573 K (1300 °C) and over a range of oxygen partial pressures of 10−11 to 10−5 atm, through equilibrating the slag with metallic copper in magnesia crucibles under a flowing Ar-CO-CO2 gas mixture. At low oxygen partial pressures, copper was found to dissolve into slag as a univalent species (CuO0.5) with a linear dependence on the oxygen partial pressure (in logarithm), with a slope of 0.23. At higher oxygen partial pressures (>10−7 atm), the data suggest a divalent copper species becomes significant (CuO) and causes the dependence on oxygen partial pressure to increase. The determination of the Fe3+/Fe2+ ratio in the slag was effected by the cuprous (Cu+) content, which acts to increase the apparent ferrous (Fe2+) content during acid digestion. A correction procedure was applied to the Fe3+/Fe2+ ratio based on the calculated Cu+ content of the slag. The procedure assumes that the activity coefficients of CuO0.5 and CuO (γCuO0.5 and γCuO) in these slags are independent of oxygen partial pressure. The calculated activity coefficients of CuO0.5 and CuO were 3.43 and 0.29, respectively. The corrected Fe3+/Fe2+ ratio had a linear dependence of 0.17 on the oxygen partial pressure over the entire oxygen partial pressure range. This agrees with similar data from the literature.