The dry oxidation of tetragonal FeS1- x mackinawite

The gradual oxidation of dry mackinawite (tetragonal FeS_{1? x} ) has been studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). The initial material and samples exposed to the air (5?min to 6?months) have been analysed. Diffraction patterns showed the slow disappearance of mackinawite with time with concomitant appearance of greigite (Fe₃S₄) and elemental sulphur (S(0)) as well as iron (oxyhydr)oxides, i.e. magnetite (Fe₃O₄) and probably goethite (α-FeOOH). After 6 months' air exposure, mackinawite and also greigite were entirely converted into elemental sulphur and iron (oxyhydr)oxide(s), indicating that greigite was an intermediate reaction product. Mössbauer spectra of samples oxidized in air appeared rather complex for interpreting what was easily conceivable in view of the association of several phases, as revealed by the diffraction patterns. The low-temperature Mössbauer spectrum obtained after 6?months air exposure was attributed to magnetite, although a mixture of magnetite and goethite was not completely excluded. XPS iron and oxygen data confirmed the formation of Fe(III) (oxyhydr)oxides at the surface after an induction period. Sulphur spectra demonstrated various oxidation states from S(-II) (monosulphide) to S(VI) (sulphate) for the longest experiments. Mackinawite in these experiments reacted mainly with adsorbed O₂ to form elemental sulphur and magnetite. Additionally, sufficient sulphur was generated to react stoichiometrically with mackinawite to produce greigite. Finally, greigite, in the longest experiments, was transformed into elemental sulphur and magnetite.