Abstract |
The rate of oxidation of iron(II) by oxygen conforms to a relationship which is first-order in the concentrations of ferrous iron and oxygen, and second-order in the concentration of hydroxide ion, at pH values between 6.0 and 7.5. The reaction proceeds relatively rapid at pH values greater than 6.5; the half-time of the reaction is 4 minutes at pH 7.0, under a partial pressure of oxygen of 0.20 atmospheres at 25 deg C. The dependence of the oxidation rate on hydroxide concentration has been observed, in this study, at pH values as low as 4.5, where the half-time has increased to approximately 300 days. At lower pH values, the dependence of the reaction rate on pH becomes less marked until at pH values below 3.5, the oxidation proceeds at a rate which is independent of pH. Field results suggest that the observed rapidity of the reaction in acidic mine waters is apparently the result of microbial catalysis. The rate-limiting step among the reactions involved in the oxidation of iron pyrite and the production of acidity in mine drainage waters is the oxygenation of ferrous iron. Oxidation of iron pyrite is by a cyclical reaction involving the slow oxygenation of iron(II) to iron(III) followed immediately by the rapid reduction of iron(III) by pyrite, generating in turn more iron(II) and acidity. (WRSIC-abstract) |