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Thermodynamics of (Zn,Fe)S sphalerite. A CVM approach with large basis clusters

Published online by Cambridge University Press:  05 July 2018

A. I. Balabin  and
R. O. Sack
A. I. Balabin
Affiliation:
Department of Geological Sciences, Box 351310, University of Washington, Seattle, WA 98195/1310, USA
R. O. Sack*
Affiliation:
Department of Geological Sciences, Box 351310, University of Washington, Seattle, WA 98195/1310, USA
*
*E-mail: [email protected]
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Abstract

We have developed a cluster variation method (CVM) model based on cuboctahedral and octahedral basis clusters containing 13 and 6 atoms, respectively, and applied it to the analysis of the thermodynamic mixing properties of (Zn,Fe)S solid solutions. The model, in which the internal energy of the lattice is approximated by next to nearest neighbour (nnn) pair interactions and many-body interactions associated with nearest neighbour (nn) equilateral triangles, describes the FeS contents of sphalerites equilibrated with pyrrhotite and pyrite, and with pyrrhotite and iron metal within experimental uncertainties. The model predicts moderate deviations from ideality; the mean values of the Lewis and Randall activity coefficient of FeS and ZnS are, 1.48 and 1.03, respectively. Predictions of the model are in qualitative agreement with cell-edge data. The model also predicts that sphalerites undergo long-range ordering to lower-symmetry structures at temperatures only slightly below those investigated experimentally, a result in agreement with inferences from an existing Mössbauer investigation of synthetic sphalerites.

More realistic models in which interactions are ascribed to larger species (nn triangular and centred square species) predict that such long-range ordering occurs at even higher temperatures and underscore the need for better characterization of the structures of (Zn,Fe)S minerals.

Keywords

sphaleritethermodynamicscluster variation methodpyrrhotitepyrite
Type
Research Article
Information
Mineralogical Magazine , Volume 64 , Issue 5 , October 2000 , pp. 923 - 943
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2000

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