Narrowly sized samples of synthetic chalcocite (Cu2S) and covellite (CuS) were leached in oxygenated acidic sulphate-chloride solutions. Chalcocite leaches via a two-stage process, the first stage being much more rapid than the second._x000D_
The apparent activation energies are 42.7 kJ/mol and 68.2 kJ/mol respectively, indicating that both stages are controlled by surface chemical reactions. The leaching of covellite is also chemically rate limited with an apparent activation energy of 77.0 kJ/mol._x000D_
The shrinking core model is able to be used to describe the leaching processes of both copper sulphides. Over 97% of copper present in chalcocite dissolved in 0.5 M H2SO4i0.5 M NaCl solution under one atmosphere pressure of oxygen at 85C in three hours from particles 36 pm in diameter while only 85% of the contained copper in covellite particles 13 pm in diameter dissolved in the same solution under the same pressure at 90C in six hours. About 99% of the sulphide sulphur in chalcocite was oxidised to elemental sulphur while only 90% of sulphide sulphur was converted to elemental sulphur during covellite leaching. The mechanism proposed for the two-stage leaching of chalcocite particles is as follows: in the first stage, cuprous ions rapidly diffuse to the external reaction surface where they lose electrons and go into solution as a complex cupric chloride ion CuCl'. The second leaching stage begins when covellite is formed at the external surface. Copper again goes into solution as the CuCl* ion. The mechanism for leaching synthetic covellite is similar to the second leaching stage for chalcocite except that the leaching rate of synthetic covellite is substantially lower than that of the newly formed 'covellite'. Elemental sulphur formed on the particle surface retards the dissolution processes during both chalcocite and covellite leaching. The presence of chloride ions is necessary if essentially all of the copper from chalcocite is to go into solution. When no chloride ions were present, the leaching rate of both newly formed and synthetic covellite was almost zero. The main role of chloride ions in both chalcocite and covellite leaching appears to be to disrupt the passivation film of sulphur on the particle surface.