Mechanistic aspects of pyrite oxidation in an oxidizing gaseous environment: an in situ HATR-IR isotope study.
The reaction of FeS2 (pyrite) with gaseous H2O, O2, and H2O/O2 was investigated using horizontal attenuated total reflection Fourier transform infrared spectroscopy (HATR-FTIR). Spectra were interpreted with the aid of hybrid molecular orbital/density functional theory calculations of sulfate-iron hydroxide clusters. Reaction of pyrite in gaseous H2O led primarily to the formation of iron hydroxide on pyrite. Exposure of the pyrite to gaseous O2 after exposure to H2O vapor led to the formation of sulfur oxyanions that included SO42-. Isotopic labeling experiments showed that after this exposure sequence the oxygen in the sulfate product was primarily derived from the H2O reactant. If, however, pyrite was exposed to gaseous O2 prior to pure H2O vapor, both SO42- and iron oxyhydroxide became significant products. Isotopic rabeling experiments using the O2-then-H2O sequence showed that the oxygen in the SO42- product was derived from both H2O and O2. The results indicate that H2O and O2 exhibit a competitive adsorption on pyrite, with H2O blocking surface sites for O2 adsorption. The extent of oxygen incorporation from either the H2O or the O2 component into the surface-bound sulfur oxyanion product appears to be a strong function of the relative concentration ratio of the reactant H2O and O2.
Usher
Courtney R
CR
Department of Chemistry, Temple University, 1901 North 13th Street, Philadelphia, Pennsylvania 19122, USA.
Paul
Kristian W
KW
Narayansamy
Jayakumar
J
Kubicki
James D
JD
Sparks
Donald L
DL
Schoonen
Martin A A
MA
Strongin
Daniel R
DR
D007501:Iron / Q000737:chemistry*; D007553:Isotope Labeling; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013440:Sulfides / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
D013440:Sulfides; D014867:Water; C011342:pyrite; D007501:Iron; D010100:Oxygen