Sulfur–selenium isomorphous substitution and morphotropic transition in the Ag3Au(Se,S)2 series

Abstract

Gold–silver sulfoselenides of the series Ag3AuSexS2–x (x = 0.25; 0.5; 0.75; 1; 1.5) were synthesized from melts on heating stoichiometric mixtures of elementary substances in evacuated quartz ampoules. According to X-ray single-crystal analysis, compound Ag3Au1Se0.5S1.5 has the structure of gold–silver sulfide Ag3AuS2 (uytenbogaardtite) with space group R3c. The volume of this compound is 1.5% larger than that of the sulfide analog. According to powder X-ray diffraction, compounds Ag3AuSe0.25S1.75 and Ag3AuSe0.75S1.25 also show trigonal symmetry. Compounds Ag3AuSeS and Ag3AuSe1.5S0.5 are structurally similar to the low-temperature modification of gold–silver selenide Ag3AuSe2 (fischesserite) with space group I4132. These data suggest the existence of two solid solutions: petzite-type cubic Ag3AuSe2–Ag3AuSeS (space group I4132) and trigonal Ag3AuSe0.75S1.25–Ag3AuS2 (space group R3c).It was found that fischesserite from the Rodnikovoe deposit (southern Kamchatka) contains 3.5–4 wt.% S. At the Kupol deposit (Chukchi Peninsula), fischesserite contains up to 2.5 wt.% S and uytenbogaardtite contains up to 5.3 wt.% Se. At the Ol’cha and Svetloe (Okhotskoe) deposits (Magadan Region), uytenbogaardtite contains up to 0.5 and 1.8 wt.% Se, respectively. Literature data on the compositions of silver–gold selenides and sulfides from different deposits were summarized and analyzed. Analysis of available data on the S and Se contents of natural fischesserite and uytenbogaardtite confirms the miscibility gap near composition Ag3AuSeS.