Rates of reaction of covellite and blaubleibender covellite with ferric iron at ph 2.0

The rates of reaction of pulverized samples (100-200 mesh) of blaubleibender covellite and covellite with 10⁻³ m ferric iron in a pH 2 solution were determined at 25, 35, and 50°C. Ferrous and cupric ion concentrations of the run solutions suggest that parallel reactions oxidized the sulfur to either elemental sulfur or to sulfate. The reaction that produces elemental sulfur is by far the fastest. The disappearance of ferric iron follows a first-order rate law which is a combination of the two first-order reactions:

-dm_Fe3+/dt = (k₁ + k₂) (A/M) m_Fe3+

where m_Fe3+ is the molal concentration of uncomplexed ferric iron, k₁ and k₂ are the rate constants and A/M is the ratio of the surface area of the reacting solid to the mass of the solution.

At 25°C the measured rate constants are 7.14 x 10⁻⁵ ± 1% sec⁻¹ for blaubleibender covellite and 9.4 x 10⁻⁴ ± 1% sec⁻¹ for covellite indicating that blaubleibender covellite reacts almost an order of magnitude faster than stoichiometric covellite under these conditions. However, the activation energies for these reactions, over the temperature interval 25 to 50°C, are the same, within the range of the reported error: 51.8 ± 6.2 kJ mol⁻¹ for blaubleibender covellite and 58.29 ± -13. 7 kJ mol⁻¹ for covellite. This suggests that the rate limiting step for both reactions is the same. The relatively high activation energies indicate surface reactions control the rate of oxidation at these temperatures.