High-temperature FeS–FeS2 solid-state transitions: Reactions of solid mackinawite with gaseous H2S

Phase transitions and reactions of non-oxidized and surface-oxidized mackinawite (FeS) in helium and H2S gas were investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). DFT was used to obtain optimized structures of the iron–sulfur phases mackinawite, hexagonal pyrrhotite, greigite, marcasite and pyrite and to determine the thermochemical properties of reactions of mackinawite with H2S to these phases. The phase transitions of mackinawite to hexagonal pyrrhotite are endothermic, while reactions to greigite, marcasite and pyrite are exothermic. The experiments show that non-oxidized mackinawite converts into hexagonal pyrrhotite (Fe9S10 first and then Fe7S8) in He and also in H2S but at a lower temperature. No further reactions can be observed under these conditions. In the case of surface-oxidized mackinawite, the extent of surface oxidation determines the course and the final product of the reaction with H2S. If the extent of surface oxidation is low, only Fe2+ is oxidized to Fe3+. Under these conditions mackinawite converts into the mixed-valence thiospinel compound greigite. In case of pronounced surface oxidation all surface Fe centers are oxidized to the Fe3+ state and S2− is oxidized to SO42−. Oxidation of sulfur is a prerequisite for the formation of pyrite.