Kinetic effects of particle-size and crystal dislocation density on the dichromate leaching of chalcopyrite

Abstract

Relatively pure, polycrystalline samples of Golden, New Mexico and Transvaal, South Africa chalcopyrite were ground and polished to fit into a density-compatible titanium alloy sandwich assembly and shock loaded (the Golden at 1.2 GPa, the Transvaal at 18 GPa peak pressure). The recovered samples were examined in the transmission electron microscope and observed to contain roughly 103 and 104 times more dislocations respectively than the natural, unshocked materials which contained roughly 107 cm−2. These materials were ground to three size fractions and leached in an acid-dichromate lixiviant at 50 and 70 °C (323 and 343 K). Corresponding size fractions were prepared from the unshocked material and leached for comparison; and these experiments were extended to a range of temperatures up to 90 °C (363 K) using a Bingham Canyon, Utah chalcopyrite. An unambiguous effect of dislocations was observed at the largest size fraction leached at 50 °C (323 K): the reaction rate constant increased from 1.44 × 10−3 to 1.62 × 10−3 to 2.73 × 10−3 min−1 for dislocation densities increasing from roughly 103 cm−2 to 1011 cm−2. A linear relationship in the leaching rate was observed between 25 and 60 °C (298 and 333 K) and the activation energy was calculated to be approximately 12 kcal/mol (50 kJ/mol). Above 60 °C (333 K) a conspicuous rate decrease was observed. This was related to a densification of the sulfur product layer, which at 50 °C (323 K) was a loose, porous precipitate while at 90 °C (363 K) it was a continuous, tenacious, glassy coating on the chalcopyrite particles. In addition, and more importantly, the high-temperature decline in leaching rate was inferred to be associated with adsorption of Cr(VI) ion which decreases with increasing temperature. The anomalous and unpredictable behavior of chalcopyrite leached in acid-dichromate lixiviant was therefore observed to be related to variations in a surface chemisorption mechanism as well as variations in the nature of the sulfur reaction product layer. These effects also mask the influence of crystal defects and other surface-related crystallographic effects in leaching.