The kinetics of oxidation
with oxygen of chalcocite, Cu2S, to CuS in buffered aqueous ammonia
at pH 10.5 at 30� can be modeled approximately by a shrinking core of Cu2S
within a thickening shell of CuxS (x ≥ 1). The Cu2S
core offers partial cathodic protection to the CuxS and diffusion of
Cu+ through CuxS controls the rate of reaction. The kinetics of oxidation
of covellite, CuS, to Cu2+, sulfur and sulfate ions in the same
solvent can be modeled by a shrinking core of CuS surrounded by a shrinking
sphere of CuyS (y < 1) which is much less effectively protected
cathodically by the CuS core. Oxidation of CuS is subject to mixed chemical and
diffusion control. Rates of oxidation of NiS and of CuS, in the presence and
absence of tetrachloroethene and ammonium sulfate, show that, whether sulfur is
a major oxidation product or not, the presence of sulfur has very little, if
any, influence on the rate or mechanism of oxidation. This is contrary to
current ideas on metal sulfide oxidation.