Stability relations of malachite and azurite

Stability relations of malachite and azurite are calculated and shown in Eh-pH diagrams, using AF (Gibbs free energy) values listed in Garrels and Christ (1965). The malachite/azurite transition is very sensitive to small chemical changes in the environment: equilibrium is reached at Pco2 = 10-a4s atm., i.e. close to normal values, whereas the precipitation of both minerals from cupric-ion-bearing solutions takes place at pH values between 6 and 8, depending CO 2 partial pressures. It is shown that stability relations of these minerals can be better explained in terms of activities of the carbonate and bicarbonate ion. Azurite can be formed only under relatively acid conditions at relatively high carbonate activities. Since the latter imply mostly basic conditions, this explains why malachite is the more common form of copper carbonate and that azurite can be formed only under rather unusual conditions. It also explains the frequent alteration of azurite into malachite, due to small changes in carbonate/bicarbonate activities. These alterations include pseudomorphs of malachite after azurite.