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29Si and 27Al MAS-NMR spectroscopy of b-eucryptite (LiAlSiO4): The enthalpy of Si,Al ordering

  • Brian L. Phillips EMAIL logo , Hongwu Xu , Peter J. Heaney and Alexandra Navrotsky
Published/Copyright: March 25, 2015
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American Mineralogist
From the journal American Mineralogist Volume 85 Issue 1

Abstract

By combining data from oxide melt solution calorimetry and 29Si MAS-NMR spectroscopy, the enthalpy for short-range Si,Al ordering in b-eucryptite (LiAlSiO4) was determined for a series of samples prepared by glass annealing. Si,Al ordered b-eucryptite gives a single 29Si NMR peak for two unresolved crystallographic sites, but two distinct 27Al resonances that differ in both chemical shift and quadrupolar coupling. Samples of β-eucryptite crystallized from glass contain additional 29Si NMR peaks, indicating significant levels of short-range Si,Al disorder. This disorder decreases exponentially with annealing time at 1173 K, from 0.55(±0.04) Al-O-Al linkages per formula unit after one hour to 0.05(±0.01) after 70.5 hours. The decrease in the concentration of Al-O-Al linkages with annealing time correlates linearly with enthalpies of drop-solution in molten lead borate, giving an enthalpy of ΔHord = -26 ± 3 kJ/mol for the reaction: Al-O-Al + Si-O-Si → 2(Si-O-Al).

Additional NMR results are presented for samples synthesized along the SiO2-LiAlSiO4 join (quartz to b-eucryptite). Solid solution samples with compositions 20 and 69 mol% quartz appear to have very few Al-O-Al linkages (<0.04 per formula unit).

Received: 1999-5-25
Accepted: 1999-9-20
Published Online: 2015-3-25
Published in Print: 2000-1-1

© 2015 by Walter de Gruyter Berlin/Boston

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  1. Eclogite-facies relics and inferred ultrahigh-pressure metamorphism in the North Dabie Complex, central-eastern China
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  3. Microstructural characterization of metamorphic magnetite crystals with implications for oxygen isotope distribution
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  7. On the cluster analysis of grains and crystals in rocks
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  13. XAFS study of Cu model compounds and Cu2+ sorption products on amorphous SiO2, γ-Al2O3, and anatase
  14. Oxidation-reduction mechanism of iron in dioctahedral smectites: I. Crystal chemistry of oxidized reference nontronites
  15. Oxidation-reduction mechanism of iron in dioctahedral smectites: II. Crystal chemistry of reduced Garfield nontronite
  16. 15N NMR study of nitrate ion structure and dynamics in hydrotalcite-like compounds
  17. 29Si and 27Al MAS-NMR spectroscopy of b-eucryptite (LiAlSiO4): The enthalpy of Si,Al ordering
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  23. The crystal structure of gearksutite, CaAlF4(OH)· H2O
  24. A new anhydrous amphibole from the Eifel region, Germany: Description and crystal structure of obertiite, NaNa2(Mg3Fe3+Ti4+)Si8O22O2
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https://doi.org/10.2138/am-2000-0117

Articles in the same Issue

  1. Eclogite-facies relics and inferred ultrahigh-pressure metamorphism in the North Dabie Complex, central-eastern China
  2. Application of INVEQ to the geothermobarometry of metamorphic rocks near a kyanite-sillimanite isograd, Mica Creek, British Columbia
  3. Microstructural characterization of metamorphic magnetite crystals with implications for oxygen isotope distribution
  4. Coexisting monazite and allanite in peraluminous granitoids of the TribečMountains, Western Carpathians
  5. Effect of alkalis, phosphorus, and water on the surface tension of haplogranite melt
  6. Direct observation of immiscibility in pyrope-almandine-grossular garnet
  7. On the cluster analysis of grains and crystals in rocks
  8. Experimental approach to constrain second critical end points in fluid/silicate systems: Near-solidus fluids and melts in the system albite-H2O
  9. Estimation and testing of standard molar thermodynamic properties of tourmaline end-members using data of natural samples
  10. An investigation of matrix effects in the analysis of fluorine in humite-group minerals by EMPA, SIMS, and SREF
  11. New data on the crystal-chemistry of fluoborite by means of SREF, SIMS, and EMP analysis
  12. Effect of aluminum on Ti-coordination in silicate glasses: A XANES study
  13. XAFS study of Cu model compounds and Cu2+ sorption products on amorphous SiO2, γ-Al2O3, and anatase
  14. Oxidation-reduction mechanism of iron in dioctahedral smectites: I. Crystal chemistry of oxidized reference nontronites
  15. Oxidation-reduction mechanism of iron in dioctahedral smectites: II. Crystal chemistry of reduced Garfield nontronite
  16. 15N NMR study of nitrate ion structure and dynamics in hydrotalcite-like compounds
  17. 29Si and 27Al MAS-NMR spectroscopy of b-eucryptite (LiAlSiO4): The enthalpy of Si,Al ordering
  18. The nuclear and magnetic structure of “white rust”—Fe(OH0.86D0.14)2
  19. In-situ study of the R3̅ to R3̅c phase transition in the ilmenite-hematite solid solution using time-of-flight neutron powder diffraction
  20. In situ X-ray diffraction investigation of lawsonite and zoisite at high pressures and temperatures
  21. A shell model for the simulation of rhombohedral carbonate minerals and their point defects
  22. Optical properties of natural and cation-exchanged heulandite group zeolites
  23. The crystal structure of gearksutite, CaAlF4(OH)· H2O
  24. A new anhydrous amphibole from the Eifel region, Germany: Description and crystal structure of obertiite, NaNa2(Mg3Fe3+Ti4+)Si8O22O2
  25. Kinoshitalite, Ba(Mg)3(Al2Si2)O10(OH,F)2, a brittle mica from a manganese deposit in Oman: Paragenesis and crystal chemistry
  26. The crystal structure of parisite-(Ce), Ce2CaF2(CO3)3
  27. High-pressure synthesis of Na2Mg6Si6O18(OH)2—a new hydrous silicate phase isostructural with aenigmatite
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