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Mixed valence of iron in minerals with cation clusters

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Abstract

The valence and distribution of iron in vivianite, lazulite, babingtonite, rockbridgeite, acmite, aegirine-augite, hedenbergite, and ilvaite were studied with optical and Mössbauer spectroscopy. Optically activated intervalence charge transfer between Fe2+ and Fe3+ in neighboring sites through common edges or faces is observed in all these minerals irrespective of the polymerization of the iron-oxygen polyhedra ranging from finite clusters to infinite structural units. However, a distinct decrease occurs in the energy of the corresponding optical absorption band with increasing number of Fe2+ and Fe3+ ions involved in the charge transfer process. Thermally activated electron delocalization between Fe2+ and Fe3+ occurs only if Fe2+ and Fe3+ occupy crystallographically equivalent or geometrically very similar neighboring sites which share common edges to form extended structural units such as the ribbon in ilvaite. If the Fe-O polyhedra form finite clusters of two, three, or four polyhedra (e.g., in vivianite, lazulite, and babingtonite, respectively) no thermally-activated mixed-valence states of iron are observed. In aegirine, extended regions of the M1 chain are statistically occupied by Fe2+ and Fe3+ giving rise to thermally-activated electron delocalization in addition to the intervalence band in the optical absorption spectrum. The intensity of the optical intervalence absorption has been measured in a number of systems: ɛ values range from 60 to 210.

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References

  • Amthauer G (1980) 57Fe Mössbauer study of babingtonite. Am Mineral 65:157–162

    Google Scholar 

  • Amthauer G, Evans BJ (1978) Single crystal and high pressure 57Fe Mössbauer studies of ilvaite, CaFe 2+2 Fe3+ (Si2O7/O/OH) at 298 K. Phys Chem Minerals 3:55–56

    Google Scholar 

  • Amthauer G, Annersten H, Hafner SS (1976) The Mössbauer spectrum of 57Fe in silicate garnets. Z Kristallogr 143:14–55

    Google Scholar 

  • Amthauer G, Langer K, Schliestedt M (1980) Thermally activated electron delocalization in deerite. Phys Chem Minerals 6:19–30

    Google Scholar 

  • Annersten H, Nyambok IO (1978) Iron distribution in aegirineaugite clinopyroxenes studied by Mössbauer effect. UUDMP Research Report No. 11, Uppsala

  • Araki T, Zoltai T (1972) Crystal structure of babingtonite. Z Kristallogr 135:355–373

    Google Scholar 

  • Austin IG, Mott NF (1970) Metallic and nonmetallic behaviour in transition metal oxides. Science 168:71–77

    Google Scholar 

  • Bauminger R, Cohen SG, Marinov A, Ofer S, Segal E (1961) Study of the low-temperature transition in magnetite and the internal fields acting on iron nuclei in some spinel ferrites using Mössbauer absorption. Phys Rev 122:1447–1450

    Google Scholar 

  • Belov NV, Mokeeva VI (1954) The crystal structure of ilvaite. Trudy Inst Kristallogr Akad Nauk SSSR 9:89–102

    Google Scholar 

  • Bence AE, Albee AL (1968) Empirical correction factors for the electron microanalysis of silicates and oxides. J Geol 76:382–403

    Google Scholar 

  • Beran A, Bittner H (1974) Untersuchungen zur Kristallchemie des Ilvaits. Tschermaks Mineral Petrogr Mitt 21:11–29

    Google Scholar 

  • Beveridge D, Day P (1979) Charge transfer in mixed-valence solids. Part 9. Preparation, characterization, and optical spectroscopy of the mixed-valence minerale voltaite (aluminum pentairon(II) tri-iron(III) dipotassium dodecasulphate 18-hydrate) and its solid solutions with cadmium(II). J C S Dalton 648–653

  • Burns RG (1970) Mineralogical applications of crystal field theory. Cambridge University Press, Cambridge

    Google Scholar 

  • Burns RG (1981) Intervalence transitions in mixed-valence minerals of iron and titanium. Ann Rev Earth Planet Sci 9:345–383

    Google Scholar 

  • Burns RG, Nolet DA, Parkin KM, McCammon CA, Schwartz KB (1979) Mixed-valence minerals of iron and titanium: correlations of structural, Mössbauer and electronic spectral data. In: Brown DB (ed) Mixed-Valence Compounds. D Reidel Publ Co, Dordrecht, pp 295–336

    Google Scholar 

  • Cameron M Papike JJ (1981) Structural and chemical variations in pyroxenes. Am Mineral 66:1–50

    Google Scholar 

  • Clark JR, Appleman DE, Papike JJ (1969) Crystal chemical characterization of clinopyroxenes based on eight new structure refinements. Mineral Soc Amer Special Paper 2:31–50

    Google Scholar 

  • Cox PA (1980) Electron transfer between exchange-coupled ions in a mixed-valency compound. Chem Phys Lett 69:340–343

    Google Scholar 

  • Dormann JL, Poullen JF (1980) Etude par spectroscopie Mössbauer de vivianites oxydees naturelles. Bull Minéral 103:633–639

    Google Scholar 

  • Dormann JL, Gaspérin M, Poullen JF (1982) Etude structurale de la séquence d'oxydation de la vivianite Fe3(PO4)2·8H2O. Bull Minéral 105:147–160

    Google Scholar 

  • Dowty E, Lindsley DH (1973) Mössbauer spectra of synthetic hedenbergite-ferrosilite pyroxenes. Am Mineral 58:850–868

    Google Scholar 

  • Evans BJ, Amthauer G (1980) The electronic structure of ilvaite and the pressure and temperature dependence of its 57Fe Mössbauer spectrum. J Phys Chem Solids 41:985–1001

    Google Scholar 

  • Faye GH (1968) The optical absorption spectra of iron in six-coordinate sites in chlorite, biotite, phlogopite and vivianite. Some aspects of pleochroism in the sheet silicates. Can Mineral 9:403–425

    Google Scholar 

  • Faye GH, Manning PG, Nickel EH (1968) The polarized optical absorption spectra of tourmaline, cordierite, chloritoid, and vivanite: ferrous-ferric electronic interaction as a source of pleochroism. Am Mineral 53:1174–1201

    Google Scholar 

  • Finger LW, Hazen KM, Hughes JM (1982) Crystal structure of monoclinic ilvaite. Carnegie Institution Year Book 81:386–388

    Google Scholar 

  • Fleet ME (1977) The crystal structure of deerite. Am Mineral 62:990–998

    Google Scholar 

  • Gerard A, Grandjean F (1971) Observations by the Mössbauer effect of an electron hopping process in ilvaite. Solid State Commun 9:1845–1849

    Google Scholar 

  • Goldman DS, Rossman GR (1977) The spectra of iron in orthopyroxene revisited: the splitting of the ground sate. Am Mineral 62:151–157

    Google Scholar 

  • Haga N, Takeuchi Y (1976) Neutron diffraction study of ilvaite. Z Kristallogr 144:161–174

    Google Scholar 

  • Hamilton WC (1958) Neutron diffraction investigation of the 119° K transition in magnetite. Phys Rev 110:1050–1057

    Google Scholar 

  • Herzenberg CL, Riley DL (1969) Oxidation states and site symmetries of iron in ilvaite using Mössbauer spectrometry. Acta Crystallogr A 25:389–391

    Google Scholar 

  • Hush NS (1967) Intervalence-transfer absorption. Part 2. Theoretical considerations and spectroscopic data. In: Prog Inorg Chem 8:391–612. Cotton FA (ed) John Wiley and Sons, New York

    Google Scholar 

  • Lindberg ML, Christ CL (1959) Crystal structure of the isostructural minerals lazulite, scorzalite, and barbosalite. Acta Crystallogr 12:695–697

    Google Scholar 

  • Litterst FJ, Amthauer G (1984) Electron delocalization in ilvaite, are reinterpretation of its 57Fe Mössbauer spectrum. Phys Chem Minerals 10:250–255

    Google Scholar 

  • Loeffler BM, Burns RG, Tossell JA (1975) Metal-metal charge transfer transitions: Interpretations of visible region spectra of the moon and lunar materials. Proc 6th Lunar Sci Conf 3:2663–2676

  • Lotgering FK, van Diepen AM (1977) Electron exchange between Fe2+ and Fe3+ ions on octahedral sites in spinels studied by means of paramagnetic Mössbauer spectra and susceptibility measurements. J Phys Chem Solids 38:565–572

    Google Scholar 

  • McCammon CA, Burns RG (1980) The oxidation mechanism of vivianite as studied by Mössbauer spectroscopy. Am Mineral 65:361–366

    Google Scholar 

  • Moore PB (1970) Crystal chemistry of the basic iron phosphates. Am Mineral 55:135–169

    Google Scholar 

  • Mori H, Ito T (1950) The structure of vivianite and symplesite. Acta Crystallogr 3:1–6

    Google Scholar 

  • Mott NF (1980) Materials with mixed valency that show a Verwey transition. Phil Mag B42:327–335

    Google Scholar 

  • Nolet DA, Burns RG (1978) Temperature dependent Fe2+-Fe3+ electron delocalization in ilvaite. Geophys Res Lett 5:821–824

    Google Scholar 

  • Nolet DA, Burns RG (1979) Ilvaite: A study of temperature dependent electron delocalization by the Mössbauer effect. Phys Chem Minerals 4:221–234

    Google Scholar 

  • Pecora WT, Fahey JJ (1947) Scorzalite and souzalite, two new phosphate minerals associated with brazilianite, Minas Gerais, Brazil. Bull Geol Soc Am 58:1216–1217

    Google Scholar 

  • Robin MB, Day P (1967) Mixed valence chemistry — a survey and classification. Adv Inorg Chem Radiochem 10:247–422

    Google Scholar 

  • Rossman GR (1975) Spectroscopic and magnetic studies of ferric iron hydroxy sulfates: intensification of color in ferric iron clusters bridged by a single hydroxide ion. Am Mineral 60:698–704

    Google Scholar 

  • Rossman GR (1980) Pyroxene spectroscopy. In: Pyroxenes 93–115. Prewitt CT (ed) Book Crafters Inc., Chelsea

    Google Scholar 

  • Smith G, (1978) Evidence for absorption by exchange-coupled Fe2+-Fe3+ pairs in the near infra-red spectra of minerals. Phys Chem Minerals 3:375–383

    Google Scholar 

  • Smith G (1980) Evidence for optical absorption by Fe2+-Fe3+ interactions in MgO: Fe. Phys Status Solidi (A) 61:K1 91

  • Smith G, Strens RGJ (1976) Intervalence-transfer absorption in some silicate, oxide, and phosphate minerals. In: The Physics and Chemistry of Minerals and Rocks. Strens RGJ (ed) John Wiley and Sons, New York, pp 583–612

    Google Scholar 

  • Takéuchi Y, Haga N, Bunno M (1983) X-ray study on polymorphism of ilvaite, HCaFe 2+2 Fe3+O2[Si2O7]. Z Kristallogr 163:267–283

    Google Scholar 

  • Vochten R, de Grave E, Stoops G (1979) Petrographic, chemical and Mössbauer study of some oxidized vivianite nodules from Retie (Province of Antwerp, Belgium). Neues Jahrb Mineral Abh 137:208–222

    Google Scholar 

  • Winchell AN, Winchell H (1951) Elements of Optical Mineralogy. John Wiley and Sons, New York

    Google Scholar 

Download references

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Authors and Affiliations

  1. Institut für Mineralogie, Universität Marburg, 3550, Marburg, West Germany

    Georg Amthauer

  2. Division of Geological and Planetary Sciences, California Institute of Technology, 91125, Pasadena, California, USA

    George R. Rossman

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  1. Georg Amthauer
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  2. George R. Rossman
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Contribution No. 3853

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Amthauer, G., Rossman, G.R. Mixed valence of iron in minerals with cation clusters. Phys Chem Minerals 11, 37–51 (1984). https://doi.org/10.1007/BF00309374

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