Silver sulfide, Ag2S, is most commonly known as the tarnish that forms on silver surfaces due to the exposure of silver to hydrogen sulfide. The mineral acanthite is a monoclinic crystalline form of Ag2S that is stable to 176°C. Upon heating above 176°C, there is a phase conversion to a body-centered cubic (bcc) form referred to as argentite. Further heating above 586°C results in conversion of the bcc phase to a face-centered cubic (fcc) phase polymorph. Both high-temperature cubic phases are solid-state silver ion conductors. In situ high-temperature X-ray diffraction was used to better understand the polymorphs of Ag2S on heating. The existing powder diffraction file (PDF) entries for the high-temperature fcc polymorph are of questionable reliability, prompting a full Rietveld structure refinement of the bcc and fcc polymorphs. Rietveld analysis was useful to show that the silver atoms are largely disordered and can only be described by unreasonably large isotropic displacement parameters or split site models.
