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Mixed-Valence Minerals of Iron and Titanium: Correlations of Structural, Mössbauer and Electronic Spectral Data

  • Chapter
Mixed-Valence Compounds

Part of the book series: NATO Advanced Study Institutes Series ((ASIC,volume 58))

Abstract

A large cariety of mixed-valence silicate and oxide minerals occur in rocks from the Earth, Moon and Meteorites, They frequently contain Fe2+ -Fe3+, Ti3+ -Ti4+ and Fe2+ -Ti4+ assemblages and often display anomalous color or opacity, high thermal and electrical conductives, and unusual spectral variations with temperature or pressure. Such properties are not attributable to transitions in single cations and indicate the presence of intervalence transitions. The intervalence transitions are observed either as charge transfer (CT) bands in the visible-near infrared region and frequently cause blue colors in FeFe2+ -Fe3+ and Fe2+ -Ti4+ bearing minerals (e.g. viviante, sapphire, dordierite, kyanite, bearing minerals (e.g. vivianite, sapphire, cordierite, kyanite glaucophane, aquamarine), or as electron decolalozation (ED) often causing opacity and semiconductor behavior (e.g. magnetite, ilvaite, deerite, riebeckite). Many of the physical and spectral properties of mixed-valence silicate and oxide minerals may be correlated with crystal structure features and site Occupancies of the metals. Structural variables which affect properties of mixed-valence oxide and silicate minerals or distorted octahedra, tetrahedra, dodecahedra), type of polyhedral linkage (e.g. face-shared, edge-shared, corner-shared) metal-oxygen (M-O) distances, metal-metal (M-M) distances, and M-O-M bond angles; and orientation and extend of linked polyhedra (e.g. isolated pairs, chains, bands, sheets; blocking by Mg2+ and AI3+ in solid solution series). These features may be used to interpret the temperature and pressure dependencies of CT bands in minerals with isolated Fe2+-Fe3+ and Fe2+-Ti4+ clustes (e.g. vivianite, sapphire, glaucophane, kyanite, cordierite, omphacite, pyroxenes, etc.), and the occurance of Fe in intermediate electronic environments in minerals with infinite chains of edge-shared Fe2+-Fe3+ polyhedra (e.g. magnetite, ilvaite, deerite, schorlomite garnets, riebeckite, and potentially aenigmatite, howieite, babingtonite).

“Since ferrous iron usually colors minerals green, and ferric iron yellow or brown, it may seem rather remarkable that the presence of both together should give rise to a blue color, as in the case of vivianite. It may be pointed out, however, that this is by no means a unique instance of such an effect. Even apart from the artificial substances, “Prussian” and “Turnbull’s” blues, which are complex cyanides containing both ferric and ferrous iron, there are several blue minerals in which the color seems explainable only on this basis. The most noteworthy of these are: crocidolite and related amphiboles; iolite; and the blue tourmaline or indicolite. Other instances may perhaps be discovered, should this subject ever be investigated as it deserves to be.” E.T. Wherry, Amer. Mineral, v.3m p.161 (1918)

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Present addresses of coauthors

  • D.A. Nolet, Material Control and Applied Research, Manufacturing and Engineering, Corning Glass Works, Corning, New York 14830,

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  • K.M. Parkin, Metal Oxidation and Corrosion, Division of Chemistry, National Research Council of Canada, Ottawa K1A 0R6, Canada

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  • C.A. McCammon, Research School of Earth Sciences, Australian National University, Canberra, ACT 2600, Australia

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  • K.M. Schwartz, Department-of Earth and Space Sciences, State University of New York, Stony Brook, New York 11794

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Authors and Affiliations

  1. Department of Earth and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, Massachusetts, 02139, USA

    Roger G. Burns, D. A. Nolet, K. M. Parkin, C. A. McCammon & K. B. Schwartz

  2. Material Control and Applied Research, Manufacturing and Engineering, Corning Glass Works, Corning, New York, 14830, USA

    D. A. Nolet

  3. Metal Oxidation and Corrosion, Division of Chemistry, National Research Council of Canada, Ottawa, K1A 0R6, Canada

    K. M. Parkin

  4. Research School of Earth Sciences, Australian National National University, Ottawa, K1A 0R6, Canada

    C. A. McCammon

  5. Department of Earth and Space Sciences, State University of New York, Stony Brook, New York, 11794, USA

    K. B. Schwartz

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  1. Roger G. Burns
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  1. Department of Chemistry, The University of Vermont, Cook Physical Science Building, Burlington, Vermont, USA

    David B. Brown

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Burns, R.G., Nolet, D.A., Parkin, K.M., McCammon, C.A., Schwartz, K.B. (1980). Mixed-Valence Minerals of Iron and Titanium: Correlations of Structural, Mössbauer and Electronic Spectral Data. In: Brown, D.B. (eds) Mixed-Valence Compounds. NATO Advanced Study Institutes Series, vol 58. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-9076-0_10

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