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Bi-Sb energetics in sulfosalts and sulfides

Published online by Cambridge University Press:  05 July 2018

S. Ghosal  and
R. O. Sack
S. Ghosal
Affiliation:
Department of Earth and Atmospheric Sciences, Purdue University, West Lafayette, IN, 47907-1397, USA
R. O. Sack*
Affiliation:
Department of Geological Sciences, Box 351310, University of Washington, Seattle, WA, 98195-1310, USA
*
* Corresponding author
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Abstract

Experimental brackets (300–450°C) on Sb-Bi partitioning between stibnite-bismuthinites (Sb,Bi)2S3 and sulfosalts in the AgSbS2–AgBiS2 binary subsystem (α-Ag(Sb,Bi)S2, β-Ag5(Sb,Bi)4I(Sb,Bi)IIS10) and extant constraints are used to define mixing properties and standard state Gibbs energies of Sb-Bi exchange reactions. They are also used to construct a phase diagram for Ag(Sb,Bi)S2 sulfosalts. We infer that the non-ideality associated with Sb-Bi mixing is largest in minerals of the β-Ag5(Sb,Bi)4I(Sb,Bi)IIS10 series, and is sufficient to produce miscibility gaps between an ordered intermediate species Ag5(Sb)4I(Bi)IIS10 and Sb- and Bi-end-members at T < 240°C (measured in terms of symmetric regular-solution-type parameters ¼WBi−SbIβ = WBi−SbIIβ ∼ 8.5 kJ/gfw). The non-ideality associated with the Sb-Bi substitution in stibnite-bismuthinite and α-Ag(Sb,Bi)S2 is ≈ 70% that in the Ag5(Sb,Bi)4I(Sb,Bi)IIS10 series (WBi−SbBS ≈ 12.0 kJ/gfw; WBi−Sbα ≈ 6.0 kJ/gfw). It is insufficient to produce exsolution at temperatures of ore deposition (T > Tc ≈ 88°C), but most likely is responsible for a preponderance in molar Sb/Bi ratios towards end-member compositions. Finally, positive Gibbs energies of the Sb-Bi exchange reactions and indicate that Bi is more compatible in stibnite-bismuthinite sulfides than in Ag(Sb,Bi)S2 sulfosalts.

Keywords

bismuthinite-stibnitesAg(Sb,Bi)S2 sulfosaltsSb-Bi energeticsordering and exchange reactions
Type
Research Article
Information
Mineralogical Magazine , Volume 63 , Issue 5 , October 1999 , pp. 723 - 733
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1999

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