Startseite Defect contributions to the heat capacities and stabilities of some chain, ring, and sheet silicates, with implications for mantle minerals
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Defect contributions to the heat capacities and stabilities of some chain, ring, and sheet silicates, with implications for mantle minerals

  • H. Wayne Nesbitt EMAIL logo , A.N. Cormack und Grant S. Henderson
Veröffentlicht/Copyright: 30. Oktober 2017
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 102 Heft 11

Abstract

At temperatures less than ~1500 K, previously published CP data demonstrate that the heat capacities of orthoenstatite, proto-enstatite, diopside, and pseudowollastonite include primarily Debye type vibrational and anharmonic contributions, whereas the alkali chain, sheet, and ring silicates, Na2SiO3, Li2SiO3, K2SiO3, and Na2Si2O5 include a third contribution. The third contribution to CP arises from defect formation due to the mobility Na, K, Li, and O2−. The contribution becomes apparent at temperatures above 700–800 K for Na and K silicates, and above 900–1000 K for Li metasilicate. With strong thermal agitation, alkali-non-bridging oxygen (NBO) bonds are ruptured with the cations exiting their structural sites to occupy interstitial sites, thereby producing intrinsic Frenkel defects, which contribute to the CP of the alkali silicates. The magnitudes of the CP defect contributions correlate inversely with cation-oxygen bond strengths, as measured by bond dissociation energies. K-O and Na-O bond strengths are weak (239 and 257 kJ/mol) and defect contributions are large for these alkali chain, ring, and sheet silicates. The greater bond strength of Li-O (341 kJ/mol) correlates with a weaker defect contribution to the CP of Li2SiO3. Mg-O and Ca-O bonds are stronger still (394 and 464 kJ/mol) and no CP defect contributions are observed for the pyroxenes and pseudowollastonite up to ~1500 K.

Above ~800 K a polymerization reaction occurs in Na2SiO3, which produces some Q3 species and free oxygen (O2− or oxide ion). The polymerization reaction annihilates an oxygen structural site so that the O2− produced must reside on non-structural sites thus producing intrinsic anionic defects. The same reactions likely occur in Na2Si2O5 and K2SiO3. Raman spectra of Na2SiO3 indicate >10% of Na+ and ~1.7% of O2−on interstitial sites at 1348 K.

Ca- and Mg-bearing mantle minerals subjected to temperature greater than ~1500 K experience the destabilizing effects of disordering (Frenkel defect formation). The minerals may respond either by changing their composition or by changing phase. An abundance of Ca and Na defects in pyroxenes, for example, likely promotes production of new components (e.g., CaAl2SiO6, NaAlSi2O6) in pyroxenes. By their production, Ca and Na defect concentrations are reduced thereby stabilizing the phases. Mg-O bond dissociation and production of intrinsic Mg2+ and O2− point defects within olivine likely destabilize it and promote the phase transition to wadsleyite at the base of the upper mantle.

Keywords: Heat capacity of silicate minerals; Frenkel defects in silicates; cation disorder; silicate mineral stability; stability of mantle minerals

Acknowledgments

The authors acknowledge the logistical support provided by their associated universities. We thank G.M. Bancroft for numerous fruitful discussions and encouragement. We gratefully acknowledge P. Richet, his colleagues and associates for their remarkably detailed measurements of the high-temperature properties of alkali and alkaline earths silicates.

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Received: 2017-2-7
Accepted: 2017-7-21
Published Online: 2017-10-30
Published in Print: 2017-11-27

© 2017 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

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https://doi.org/10.2138/am-2017-6103
Schlagwörter für diesen Artikel
Heat capacity of silicate minerals; Frenkel defects in silicates; cation disorder; silicate mineral stability; stability of mantle minerals

Artikel in diesem Heft

  1. Highlights and Breakthroughs
  2. Rutile: A novel recorder of high-fo2 fluids in subduction zones
  3. Highlights and Breakthroughs
  4. Granites and rhyolites: Messages from Hong Kong, courtesy of zircon
  5. Review
  6. Do Fe-Ti-oxide magmas exist? Probably not!
  7. Special Collection: Biomaterials—Mineralogy Meets Medicine
  8. Calcium (Ti,Zr) hexaorthophosphate bioceramics for electrically stimulated biomedical implant devices: A position paper
  9. Special Collection: Water in Nominally Hydrous and Anhydrous Minerals
  10. Raman spectroscopy of water-rich stishovite and dense high-pressure silica up to 55 GPa
  12. Tracking the evolution of Late Mesozoic arc-related magmatic systems in Hong Kong using in-situ U-Pb dating and trace element analyses in zircon
  14. Defect contributions to the heat capacities and stabilities of some chain, ring, and sheet silicates, with implications for mantle minerals
  16. Phase transition in SiC from zinc-blende to rock-salt structure and implications for carbon-rich extrasolar planets
  18. Non-destructive, multi-method, internal analysis of multiple inclusions in a single diamond: First occurrence of mackinawite (Fe,Ni)1+xS
  20. The fate of ammonium in phengite at high temperature
  22. Parameterized lattice strain models for REE partitioning between amphibole and silicate melt
  24. Unusual replacement of Fe-Ti oxides by rutile during retrogression in amphibolite-hosted veins (Dabie UHP terrane): A mineralogical record of fluid-induced oxidation processes in exhumed UHP slabs
  26. Crystallization experiments in rhyolitic systems: The effect of temperature cycling and starting material on crystal size distribution
  28. Dolomite dissociation indicates ultra-deep (>150 km) subduction of a garnet-bearing dunite block (the Sulu UHP terrane)
  30. Microscopic strain in a grossular-pyrope solution anti-correlates with excess volume through local Mg-Ca cation arrangement, more strongly at high Ca/Mg ratio
  32. Ferruginous seawater facilitates the transformation of glauconite to chamosite: An example from the Mesoproterozoic Xiamaling Formation of North China
  34. Charleshatchettite, CaNb4O10(OH)2·8H2O, a new mineral from Mont Saint-Hilaire, Québec, Canada: Description, crystal-structure determination, and origin
  36. New Mineral Names
  38. Erratum
  39. Book Review
  40. Non-Traditional Stable Isotopes
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