V oxidation state and coordination number in silicate glasses by XAS
-
Gabriele Giuli
,
Eleonora Paris
Abstract
The local structure of vanadium (V)in synthetic glasses of basaltic composition has been studied by means of high-resolution V K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to obtain quantitative data on <V-O> distances, V coordination number (CN), and oxidation state. The compositions and experimental conditions were chosen so as to verify the effect of bulk-glass composition (using a diopside-anorthite composition, a sodium disilicate glass, and an iron-titanium-bearing basaltic glass) and V content (from 0.1 to 5 V2O5 wt%) on the structural role of V in these glasses.
The combined analysis of high-resolution XANES spectra and EXAFS data indicate that on average, the Fe-free glasses synthesized in air show vanadium in the V5+ state, mainly in tetrahedral coordination (less than 20% [5]V5+) and with <V-O> distances of 1.697 (± 0.020) Å, in agreement with the values found for tetrahedral V in minerals. In contrast, the Fe-bearing basaltic glasses display a mixture of V5+ in fourfold and fivefoldcoordination, 40% [4]V5+-60% [5]V5+ in proportion, and the EXAFS-derived distances and coordination numbers are in agreement with this interpretation. No significant changes in the V local structure were found in the glasses analyzed as a function of V-contents in the 0.1 to 5 V2O5 wt% range. The data obtained suggest that the structural role of vanadium in these melts is rather insensitive to bulk composition, in terms of V and alkali content, but can be strongly affected by the presence of other transition elements, e.g., Fe3+ competing with V to enter the tetrahedral framework.
© 2015 by Walter de Gruyter Berlin/Boston
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Articles in the same Issue
- First-principle study of polytype structures of 1:1 dioctahedral phyllosilicates
- Calorimetry of liquids in the system Na2O-Fe2O3-SiO2
- A Mössbauer study of the oxidation state of Fe in silicate melts
- Nanometer-scale measurements of Fe3+/ΣFe by electron energy-loss spectroscopy: A cautionary note
- The most reduced rock from the moon, Apollo 14 basalt 14053: Its unique features and their origin
- Quantitative analysis of ammonium in biotite using infrared spectroscopy
- Lizardite-chlorite structural relationships and an inferred high-pressure lizardite polytype
- V oxidation state and coordination number in silicate glasses by XAS
- Structure of the fluorapatite (100)-water interface by high-resolution X-ray reflectivity
- Origin of diffuse superstructure reflections in labuntsovite-group minerals
- Isosymmetric structural phase transition of orthoenstatite: Molecular dynamics simulation
- Crystal nucleation in hydrous rhyolite: Experimental data applied to classical theory
- Investigation of polytypes in lepidolite using electron back-scattered diffraction
- Iron partitioning between basaltic melts and clinopyroxene as a function of oxygen fugacity
- The synthesis of zeolite-P, Linde Type A, and hydroxysodalite zeolites from paper sludge ash at low temperature (80 °C): Optimal ash-leaching condition for zeolite synthesis
- High-pressure viscometry of polymerized silicate melts and limitations of the Eyring equation
- Biological control on calcite crystallization: AFM investigation of coccolith polysaccharide function
- Order parameter variation through the C2/m-P21/m phase transition in cummingtonite
- Arsenate sorption on schwertmannite
- Evidence on the structure of synthetic schwertmannite
- Crystal-chemical characterization of tourmalines from the English Lake District: Electron-microprobe analyses and Mössbauer spectroscopy
- Crystal chemistry and paragenesis of compositionally unique (Al-, Fe-, Nb-, and Zr-rich) titanite from Afrikanda, Russia
- Site distribution of Fe2+and Fe3+in the axinite mineral group: New crystal-chemical formula
- Epidote-rich talc-kyanite-phengite eclogites, Sulu terrane, eastern China: P-T-fO₂estimates and the significance of the epidote-talc assemblage in eclogite
- Quantitative mineralogy of the Yukon River system: Changes with reach and season, and determining sediment provenance
- Exsolution of thortveitite, yttrialite, and xenotime during low-temperature recrystallization of zircon from New Caledonia, and their significance for trace element incorporation in zircon
- Mineralogical characterization and genesis of hydrothermal Mn oxides from the flank of the Juan the Fuca Ridge
- Synchrotron X-ray diffraction study of the structure of shafranovskite, K2Na3(Mn,Fe,Na)4[Si9(O,OH)27](OH)2⋅nH2O, a rare manganese phyllosilicate from the Kola peninsula, Russia
- Letter. Coupled cation and oxygen-isotope exchange between alkali feldspar and aqueous chloride solution
