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Zn-O tetrahedral bond length variations in normal spinel oxides

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Published/Copyright: April 2, 2015
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American Mineralogist
From the journal American Mineralogist Volume 96 Issue 4

Abstract

Six synthetic single crystals of spinel phases with different compositions along the ZnAl2O4-ZnCr2O4 solid solution were structurally and chemically characterized by X-ray diffraction and electron microprobe techniques. As predicted, unit-cell parameters and octahedral bond lengths (M-O) increase with increasing replacement of Al3+ by Cr3+. Despite the constant occupancy of the T site by Zn, also the tetrahedral bond length TZn-O shows significant variations along this binary. These variations are positively correlated with variations in M-O bond lengths.

The present data in conjunction with data from literature provide a basis for quantitative analyses of the variation in TZn-O in normal spinel structures. A negative correlation between TZn-O and the ionic potential at M (MIP) suggests that increasing MIP is related to a stronger electrostatic cation-cation repulsion across the shared octahedral edge M(O-O)shared of the structure. An observed negative correlation between MIP and M(O-O)shared suggests that a decrease of M(O-O)shared provides a more efficient shielding effect to reduce the octahedral cation interactions.

In normal ZnB2O4 spinels (where B = Al3+, Cr3+, Ga3+, V3+, Fe3+, and Mn3+) cations with a smaller size provides a higher charge density. Increasing charge density at the M site causes shortening of M(O-O)shared, which in turn results in shorter TZn-O bond length. In general, variations in TZn-O are required by the structure to better provide an oxygen shielding effect to the octahedral cationcation repulsion.

Keywords : Crystal structure; spinel; XRD data; chemical analysis; ZnAl2O4; ZnCr2O4
Received: 2010-9-22
Accepted: 2010-11-15
Published Online: 2015-4-2
Published in Print: 2011-4-1

© 2015 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2011.3696
Keywords for this article
Crystal structure; spinel; XRD data; chemical analysis; ZnAl2O4; ZnCr2O4

Articles in the same Issue

  1. Roebling Medal Lecture. The three partners of metamorphic petrology
  2. Relationship between structure, morphology, and carbon isotopic composition of graphite in marbles: Implications for calcite-graphite carbon isotope thermometry
  3. Crystal structure, mosaicity, and strain analysis of Hawaiian olivines using in situ X-ray diffraction
  4. Characterization of deep weathering and nanoporosity development in shale—A neutron study
  5. Structural water in ferrihydrite and constraints this provides on possible structure models
  6. Critical evaluation of the revised akdalaite model for ferrihydrite
  7. Neutron diffraction study of hydrogen in birnessite structures
  8. Pressless split-sphere apparatus equipped with scaled-up Kawai-cell for mineralogical studies at 10–20 GPa
  9. Dislocation microstructures in majorite garnet experimentally deformed in the multi-anvil apparatus
  10. Density of carbonated peridotite magma at high pressure using an X-ray absorption method
  11. Stability and bulk modulus of Ni3S, a new nickel sulfur compound, and the melting relations of the system Ni-NiS up to 10 GPa
  12. Far-infrared spectra of synthetic [4][(Al2-xGax)(Si2–yGey)](OH,OD,F)2-kinoshitalite: Characterization and assignment of interlayer Ba-Oinner and Ba-Oouter stretching bands
  13. High-temperature elasticity of polycrystalline orthoenstatite (MgSiO3)
  14. Anatomy of a metabentonite: Nucleation and growth of illite crystals and their coalescence into mixed-layer illite/smectite
  15. Zn-O tetrahedral bond length variations in normal spinel oxides
  16. A new thermodynamic analysis of the intergrowth of hedenbergite and magnetite with Ca-Fe-rich olivine
  17. Raman spectroscopic investigations of some Tl-sulfosalt minerals containing pyramidal (As,Sb)S3 groups
  18. A first record of strong structural relaxation of TO4 tetrahedra in a spinel solid solution
  19. The high-pressure behavior of orthorhombic amphiboles
  20. XAS determination of the Fe local environment and oxidation state in phonolite glasses
  21. Chemical variation and significance of micas from the Fregeneda-Almendra pegmatitic field (Central-Iberian Zone, Spain and Portugal)
  22. Light-induced molecular change in HgI2·As4S4: Evidence by single-crystal X-ray diffraction and Raman spectroscopy
  23. Low-temperature electron paramagnetic resonance studies on natural calumetite from Khetri copper mine, Rajasthan, India
  24. Chromatite and its Cr3+- and Cr6+-bearing precursor minerals from the Nabi Musa Mottled Zone complex, Judean Desert
  25. Hazenite, KNaMg2(PO4)2⋅14H2O, a new biologically related phosphate mineral, from Mono Lake, California, U.S.A.
  26. The fractional latent heat of crystallizing magmas
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