Quick Search:    advanced search

GSW Home   GeoRef Home   My GSW Alerts   Contact GSW   About GSW   Journals List   Help

This Article Figures Only Full Text Full Text (PDF) Alert me when this article is cited Alert me if a correction is posted Citation Map Services Email this article to a friend Similar articles in this journal Similar articles in Web of Science Alert me to new issues of the journal Download to citation manager Citing Articles Citing Articles via HighWire Citing Articles via Web of Science (4) Citing Articles via Google Scholar Google Scholar Articles by Kyono, A. Articles by Kimata, M. Search for Related Content GeoRef GeoRef Citation

Structural variations induced by difference of the inert pair effect in the stibnite-bismuthinite solid solution series (Sb,Bi)₂S₃

¹ Laboratory for Entrepreneurship, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8573, Japan
² Institute of Geoscience, University of Tsukuba, Tennodai 1-1-1, Tsukuba, Ibaraki, 305-8571, Japan

Correspondence: ^* E-mail: kyono{at}arsia.geo.tsukuba.ac.jp

Structural refinements of single crystal X-ray diffraction data for synthetic (Sb,Bi)₂S₃ solid solutions revealed structural variations in the stibnite (Sb₂S₃)-bismuthinite (Bi₂S₃) series. Coordination environments of the M cations are (3 + 4)-fold for the M1 site and (5 + 2)-fold for the M2 site. For the M1 and M2 polyhedra, the short M-S bond lengths increase constantly with increasing Bi concentration, whereas the long M-S bond lengths decrease continuously. The S-M-S interatomic angles interposing lone-pair electrons increase continuously from stibnite to bismuthinite. Stereochemical activity of the lone-pair electrons induces configurational changes of ligands around the M cations from elongated ellipsoidal coordinations to spheroidal ones. Substitution of Bi³⁺ for Sb³⁺ in the solid solution expands the basic building block, which causes linear increase of the b lattice parameter with slight positive deviation from Vegard’s law. This feature is ascribed to order-disorder with concentration of Sb at the M1 site and Bi at the smaller M2 site. Furthermore, increased Bi content engenders both expansion of the basic building block and contraction of intervals between these blocks, contributing to smaller changes in the a and c lattice parameters than in the b lattice parameter. The M2 polyhedra expand relative to the M1 polyhedra with increasing Bi content because the large Bi cation is concentrated at the smaller M2 site. One striking characteristic of (Sb,Bi)₂S₃ crystal structures is that geometries of central M cation and ligand atoms can be adapted flexibly to transformation of stereochemical activity from 5s² lone-pair electrons to Bi 6s² lone-pair electrons by altering the centroid-central atom distance and by changing angles of the centroid-central atom to the a axis.

This article has been cited by other articles:

				S. Kharbish, E. Libowitzky, and A. Beran Raman spectra of isolated and interconnected pyramidal XS3 groups (X = Sb,Bi) in stibnite, bismuthinite, kermesite, stephanite and bournonite European Journal of Mineralogy, April 1, 2009; 21(2): 325 - 333. [Abstract] [Full Text] [PDF]

				A. Y. Barkov, R. F. Martin, L. Shi, W. LeBarge, and Y. Fedortchouk OSCILLATORY ZONING IN STANNIFEROUS HEMATITE AND ASSOCIATED W- AND Bi-RICH MINERALS FROM CANADIAN CREEK, YUKON, CANADA Can Mineral, February 1, 2008; 46(1): 59 - 72. [Abstract] [Full Text] [PDF]

				E. Makovicky Crystal Structures of Sulfides and Other Chalcogenides Reviews in Mineralogy and Geochemistry, January 1, 2006; 61(1): 7 - 125. [Full Text] [PDF]

				R. O. Sack and D. S. Ebel Thermochemistry of Sulfide Mineral Solutions Reviews in Mineralogy and Geochemistry, January 1, 2006; 61(1): 265 - 364. [Full Text] [PDF]