Home Defect contributions to the heat capacities and stabilities of some chain, ring, and sheet silicates, with implications for mantle minerals
Article
Licensed
Unlicensed Requires Authentication

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 and Grant S. Henderson
Published/Copyright: October 30, 2017
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 102 Issue 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.

References cited

Anderson, O.L. (1967) Equation for thermal expansivity in planetary interiors. Journal of Geophysical Research, 72, 3661–3668.10.1029/JZ072i014p03661Search in Google Scholar

Angel, R.J., and Jackson, J.M. (2002) Elasticity and equation of state of orthoenstatite, MgSiO3. American Mineralogist, 87, 558–561.10.2138/am-2002-0419Search in Google Scholar

Ashbrook, S.E., Berry, A.J., Hibberson, W.O., Steuernagel, S., and Wimperis, S. (2005) High-resolution 17O MAS NMR spectroscopy of forsterite (α-Mg2SiO4), wadsleyite (β-Mg2SiO4), and ringwoodite (γ-Mg2SiO4). American Mineralogist, 90, 1861–1870.10.2138/am.2005.1915Search in Google Scholar

Berezhnoi, G.V., and Boiko, G.G. (2005) Defects and oxygen diffusion in metasilicate melts, molecular dynamics simulation. Glass Physics and Chemistry, 31, 145–154.10.1007/s10720-005-0036-6Search in Google Scholar

Beyer, R.P., Ferrante, M.J., Brown, R.R., and Daut, G.E. (1979) Thermodynamic properties of potassium metasilicate and disilicate. United States Bureau of Mines, Report of Investigations, 8410.Search in Google Scholar

Borg, R.J., and Dienes, G.J. (1992) The Physical Chemistry of Solids, 584 p. Academic Press.Search in Google Scholar

Born, M., and von Kármán, T. (1912) Über Schwingungen in Raumgittern. Physikalische Zeitschrift, 13, 297–309.Search in Google Scholar

Bouhfid, M.A., Gruener, G., Mysen, B.O., and Richet, P. (2002) Premelting and calcium mobility in gehlenite (Ca2Al2SiO7) and pseudowollastonite (CaSiO3). Physics and Chemistry of Minerals, 29, 655–662.10.1007/s00269-002-0276-0Search in Google Scholar

Chopelas, A. (2000) Thermal expansivity of mantle relevant magnesium silicates derived from vibrational spectroscopy at high pressure. American Mineralogist, 85, 270–278.10.2138/am-2000-2-301Search in Google Scholar

Cormack, A.N., Du, J., and Zeitler, T.R. (2002) Alkali ion migration mechanisms in silicate glasses probed by molecular dynamics simulations. Physical Chemistry and Chemical Physics, 4, 3193–3197.10.1039/b201721kSearch in Google Scholar

Courtial, P., Téqui, C., and Richet, P. (2000) Thermodynamics of diopside, anorthite, pseudowollastonite, CaMgGeO4 olivine, and åkermanite up to near the melting point. Physics and Chemistry of Minerals, 27, 242–250.10.1007/s002690050253Search in Google Scholar

Debye, P. (1912) Zur theorie der spezifischen warmen. Annalen der Physik, 39, 789–839.10.1002/andp.19123441404Search in Google Scholar

Dimanov, A., and Ingrin, J. (1995) Premelting and high-temperature diffusion of Ca in synthetic diopside: An Increase of the Cation Mobility. Physics and Chemistry of Minerals, 22, 437–442.10.1007/BF00200321Search in Google Scholar

Dimanov, A., and Jaoul, O. (1998) Calcium self-diffusion in diopside at high temperature: implications for transport properties. Physics and Chemistry of Minerals, 26, 116–127.10.1007/s002690050168Search in Google Scholar

Einstein, A. (1907) Die plancksche theorie der strahlung und die theorie der spezifischen warmen. Annalen der Physik, 22, 180–190.10.1002/andp.19063270110Search in Google Scholar

Farnan, I., and Stebbins, J.F. (1990) High-temperature 29Si NMR investigation of solid and molten silicates. Journal of the American Chemical Society, 112, 32–39.10.1021/ja00157a008Search in Google Scholar

Frost, D. (2008) The upper mantle and transition zone. Elements, 4, 171–176.10.2113/GSELEMENTS.4.3.171Search in Google Scholar

George, A.M., Richet, P., and Stebbins, J.F. (1998) Cation dynamics and premelting in lithium metasilicate (Li2SiO3) and sodium metasilicate (Na2SiO3): A high-temperature NMR study. American Mineralogist, 83, 1277–1284.10.2138/am-1998-11-1216Search in Google Scholar

Ghose, S., Schomaker, V., and McMullan, R.K. (1986) Enstatite, Mg2Si206: A neutron diffraction refinement of the crystal structure and a rigid-body analysis of the thermal vibration. Zeitschrift für Kristallographie, 176, 159–175.10.1524/zkri.1986.176.3-4.159Search in Google Scholar

Ghose, S., Choudhury, N. Chaplot, S.L., and Rao, K.R. (1991) Phonon density of states and thermodynamic properties of minerals. In S.K. Saxena, Ed., Thermodynamic Data: Systematics and Estimation, chap. 11, p. 283–314. Springer-Verlag.10.1007/978-1-4612-2842-4_11Search in Google Scholar

Grimvall, G. (2001) Dependence of thermodynamic properties on atomic masses and bonding in solids. In C.A. Geiger, Ed., Solid Solutions in Silicate and Oxide Systems, 3, Chapter 2, p. 11–36. Eötvös University Press, Budapest.10.1180/EMU-notes.3.2Search in Google Scholar

Grüneisen, E. (1912) Theorie des festen Zustandes einatomiger Elelmente. Annalen der Physik, 39, 257–306.10.1002/andp.19123441202Search in Google Scholar

Grüneisen, E. (1926) Zustand des festen Körpers. Handbuch der Physik, 1, 1–52.10.1007/978-3-642-99531-6_1Search in Google Scholar

Hesse, K.F. (1977) Refinement of the crystal structure of lithium polysilicate. Acta Crystallographica, B33, 901–902.10.1107/S0567740877004932Search in Google Scholar

Hofmeister, A.M., and Mao, H.-K. (2002) Redefinition of the mode Grüneisen parameter for polyatomic substances and thermodynamic implications. Proceedings of the National Academy of Sciences, 99, 559–564.10.1073/pnas.241631698Search in Google Scholar PubMed PubMed Central

Huheey, J.E., Keiter, E.A., and Keiter, R.L. (1993) Inorganic Chemistry, 964 p. Harper-Collins.Search in Google Scholar

Ita, J., and Stixrude, L. (1992) Petrology, elasticity, and composition of the mantle transition zone. Journal of Geophysical Research, 97, 6849–6866.10.1029/92JB00068Search in Google Scholar

Jackson, J.M., Palko, J.W., Andrault, D., Sinogeikin, S.V., Lakshtanov, D.L., Wang, J., Bass, J.D., and Zha, C.-S. (2003) Thermal expansion of natural orthoenstatite to 1473 K. European Journal of Mineralogy, 15, 469–473.10.1127/0935-1221/2003/0015-0469Search in Google Scholar

Jeanloz, R., and Thompson, A.B. (1983) Phase transitions and mantle discontinuities. Reviews of Geophysics and Space Physics, 21, 51–74.10.1029/RG021i001p00051Search in Google Scholar

Katsura, T., Yamada, H., Nishikawa, O., Song, M., Kubo, A., Shinmei, T., Yokoshi, S., Aizawa, Y., Yoshino, T., Walter, M.J., Ito, E., and Funakoshi, K. (2004) Olivine-wadsleyite transition in the system (Mg,Fe)2SiO4. Journal of Geophysical Research, 109, B02209.10.1029/2003JB002438Search in Google Scholar

Kelley, K.K. (1960) Contribution to the data on theoretical metallurgy: XII. High-temperature heat content, heat-capacity and entropy data for the elements and inorganic compounds. Bureau of Mines Bulletin 584. U.S. Government Printing Office, Washington, 163 p.Search in Google Scholar

Kieffer, S.W. (1980) Thermodynamics and lattice vibrations of minerals: Application to chain and sheet silicates and orthosilicates. Reviews of Geophysics and Space Physics, 18, 862–886.10.1029/RG018i004p00862Search in Google Scholar

Kieffer, S.W. (1982) Thermodynamics and lattice vibrations of minerals: 5. Applications to phase equilibria, isotopic fractionation, and high-pressure thermodynamic properties. Reviews of Geophysics and Space Physics, 20, 827–849.10.1029/RG020i004p00827Search in Google Scholar

Krupka, K.M., Hemingway, B.S., Robie, R.A., and Kerrick, D.M. (1985) High-temperature heat capacities and derived thermodynamic properties of anthophyllite, diopside, dolomite, enstatite, bronzite, talc, tremolite, and wollastonite. American Mineralogist, 70, 261–271.Search in Google Scholar

Massa, N.E., Ullman, F.G., and Hardy, J.R. (1983) Interpretation of anomalies in the Raman spectrum of K2SeO4 in terms of oxygen sublattice disorder. Physical Review B, 27, 1523–1540.10.1103/PhysRevB.27.1523Search in Google Scholar

Naylor, B.F. (1945) High-temperature heat contents of sodium metasilicate and sodium disilicate. Journal of the American Chemical Society, 67, 466–467.10.1021/ja01219a030Search in Google Scholar

Nesbitt, H.W., Bancroft, G.M., Henderson, G.S., Sawyer, R., and Secco, R.A. (2015) Direct and indirect evidence for free oxygen (O2−) in MO-silicate glasses and melts (M = Mg, Ca, Pb). American Mineralogist, 100, 2566–2578.10.2138/am-2015-5336Search in Google Scholar

Nesbitt, H.W., Bancroft, G.M., Henderson, G.S., Richet, P., and O’Shaughnessy, C. (2017) Melting, crystallization and the glass transition: toward a unified description for silicate phase transitions. American Mineralogist, 102, 412–420.10.2138/am-2017-5852Search in Google Scholar

Pandolfo, F., Cámara, F., Domeneghetti, M.C., Alvaro, M., Nestola, F., Karato, S.-I., and Amulele, G. (2015) Volume thermal expansion along the jadeite–diopside join. Physics and Chemistry of Minerals, 42, 1–14.10.1007/s00269-014-0694-9Search in Google Scholar

Pitzer, K.S., and Brewer, L. (1961) Thermodynamics, 723 p. McGraw-Hill.Search in Google Scholar

Richet, P., and Fiquet, G. (1991) High-temperature heat capacity and premelting of minerals in the system MgO-CaO-Al2O3-SiO2. Journal of Geophysical Research, 96, 445–456.10.1029/90JB02172Search in Google Scholar

Richet, P., Bottinga, Y., and Téqui, C. (1984) Heat capacity of sodium silicate liquids. Journal of the American Ceramics Society, 67, C6–C8.10.1111/j.1151-2916.1984.tb19155.xSearch in Google Scholar

Richet, P., Leclerc, F., and Benoist, L. (1993) Melting of forsterite and spinel, with implications for the glass transition of Mg2SiO4 liquid. Geophysical Research Letters, 20, 1675–1678.10.1029/93GL01836Search in Google Scholar

Richet, P., Ingrin, J., Mysen, B.O., Courtial, P., and Gillet, P. (1994) Premelting effects in minerals: an experimental study. Earth and Planetary Science Letters, 121, 589–600.10.1016/0012-821X(94)90093-0Search in Google Scholar

Richet, P., Mysen, B.O., and Andrault, D. (1996) Melting and premelting of silicates: Raman spectroscopy and X-ray diffraction of Li2SiO3 and Na2SiO3. Physics and Chemistry of Minerals, 23, 157–172.10.1007/BF00220727Search in Google Scholar

Richet, P., Mysen, B.O., and Ingrin, J. (1998) High-temperature X-ray diffraction and Raman spectroscopy of diopside and pseudowollastonite. Physics and Chemistry of Minerals, 25, 401–414.10.1007/s002690050130Search in Google Scholar

Sawyer, R., Nesbitt, H.W., Bancroft, G.M., Thibault, Y., and Secco, R.A. (2015) Spectroscopic studies of oxygen speciation in potassium silicate glasses and melts. Canadian Journal of Chemistry, 93, 60–73.10.1139/cjc-2014-0248Search in Google Scholar

Saxena, S.K., Chatterjee, N., Fei, Y., and Shen, G., and others. (1993) Thermodynamic Data of Oxides and Silicates, p. 386–387. Springer-Verlag, Berlin.10.1007/978-3-642-78332-6Search in Google Scholar

Sen, S., and Tangeman, J. (2008) Evidence for anomalously large degree of polymerization in Mg2SiO4 glass and melt. American Mineralogist, 93, 946–949.10.2138/am.2008.2921Search in Google Scholar

Slater, J.C. (1963) Introduction to Chemical Physics, 1st paperback ed., 521 p. McGraw-Hill.Search in Google Scholar

Speight, J.G. (2005) Lange’s Handbook of Chemistry, 70th ed., Table 4.11, 4.41–4.51. McGraw Hill.Search in Google Scholar

Stebbins, J.F. (1991) NMR evidence for five-coordinated silicon in silicate glass at atmospheric pressure. Nature, 351, 638–639.10.1038/351638a0Search in Google Scholar

Téqui, C., Grinspan, P., and Richet, P. (1992) Thermodynamic properties of alkali silicates: Heat capacity of Li2SiO3 and lithium-bearing melts. Journal of the American Ceramic Society, 75, 2601–2604.10.1111/j.1151-2916.1992.tb05621.xSearch in Google Scholar

Thiéblot, L., Téqui, C., and Richet, P. (1999) High-temperature heat capacity of grossular (Ca3Al2Si3O12), enstatite (MgSiO3), and titanite (CaTiSiO5). American Mineralogist, 84, 848–855.10.2138/am-1999-5-618Search in Google Scholar

Voronko, Yu.K., Sobol, A.A., and Shukshin, V.E. (2006) Raman spectra and structure of silicon–oxygen groups in crystalline, liquid, and glassy Mg2SiO4. Inorganic Materials, 42, 981–988.10.1134/S002016850609010XSearch in Google Scholar

Werthmann, R., and Hoppe, R. (1981) Über K2SiO3—das erste cyclotrisilicat eines alkalimetalls sowie Rb2SiO3, Cs2SiO3, Rb2GeO3 und Cs2GeO3. Revue de Chimie Minérale, 18, 593–607.Search in Google Scholar

Yang, H., and Ghose, S. (1994) Thermal expansion, Debye temperature and Grüneisen parameter in synthetic (Fe, Mg)SiO3 orthopyroxenes. Physical Chemistry of Minerals, 20, 575–586.10.1007/BF00211853Search in Google Scholar

Zhao, Y., Schiferl, D., and Shankland, T.J. (1995) High P-T single-crystal X-ray diffraction study of thermoelasticity of MgSiO3 orthopyroxene. Physics and Chemistry of Minerals, 22, 393–398.10.1007/BF00213337Search in Google Scholar

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

Articles in the same Issue

  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
https://doi.org/10.2138/am-2017-6103
Keywords for this article
Heat capacity of silicate minerals; Frenkel defects in silicates; cation disorder; silicate mineral stability; stability of mantle minerals

Articles in the same Issue

  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
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 28.9.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2017-6103/html
Scroll to top button