Abstract
Published measurements of sulfur vapor pressure and silver electromotive force were used to determine thermodynamic properties of silver sulfide above 379 K. They were Gibbs–Duhem integrated to estimate the formation properties of stoichiometric Ag 2S of fcc, bcc, and monoclinic crystal structures. Statistical thermodynamics was applied to estimate free energies and find possible atom arrangements in off-stoichiometric silver sulfide. Theoretical calculations show that silver vacancies and atoms may be in quasi-chemical equilibrium between tetrahedral and octahedral sites in the fcc structure and between two states of atoms within tetrahedral sites in the bcc structure and within octahedral sites in the monoclinic structure. A strong indication is that vacancy clusters should predominate, each containing four-atom vacancies in the fcc phase and three-atom vacancies in the bcc phase.
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