Effect of pH on Aqueous Se(IV) Reduction by Pyrite
Résumé
Interaction of aqueous Se(IV) with pyrite was investigated using persistently stirred batch reactors under O2-free (<1 ppm) conditions at pH ranging from 4.5 to 6.6. Thermodynamic calculations, an increase in pH during the experiments, and spectroscopic observation indicate that the reduction of aqueous Se(IV) by pyrite is dominated by the following reaction: FeS2 + 3.5HSeO3− + 1.5H+ = 2SO42− + Fe2+ + 3.5Se(0) + 2.5H2O. The released Fe(II) was partitioned between the bulk solution and pyrite surface at pH ≈ 4.5 and 4.8, with the Fe2+ density at pyrite-solution interface about 4 orders of magnitude higher than that in the bulk solution, while iron oxyhydroxide precipitated at pH ≈ 6.6, resulting in the decrease of dissolved iron. In the Se(IV) concentration range of the experiments, aqueous Se(IV) reduction rate follows the pseudofirst order which is in the form of ln mSe(IV) = −k′t + ln mSe(IV)0, where k′ is apparent rate constant combining the rate constant k and pyrite surface area to mass of solution ratio (A/M). And the aqueous Se(IV) reduction rate constant for a standard system (k) with 1 m2 pyrite surface area per 1 kg solution was obtained to be 1.65 × 10−4 h−1, 3.28 × 10−4 h−1, and 4.76 × 10−4 h−1 at pH around 4.5, 4.8, and 5.1, respectively. The positive correlation between reaction rate and pH disagrees with the theories that protons are consumed when HSeO3− is reduced to Se0, and negative charge density on pyrite surface increases as pH increases. Thus, a ferrous iron mediated electron transfer mechanism is proposed to operate during the reduction of aqueous Se(IV) by pyrite. pH and iron concentration affect significantly on Se(IV) reaction rate and reaction product.