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Thermodynamic behavior and properties of katoite (hydrogrossular): A calorimetric study

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Published/Copyright: April 2, 2015
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American Mineralogist
From the journal American Mineralogist Volume 97 Issue 7

Abstract

The low-temperature heat capacity behavior of synthetic katoite, Ca3Al2H12O12, was investigated for the first time using microcalorimetry. The sample was synthesized hydrothermally in Au capsules at 250 °C and 3 kb water pressure. X-ray powder measurements show that about 98-99% katoite was obtained. Heat capacities were measured with a commercially designed relaxation calorimeter between 5 and 300 K on a milligram-sized sample and around ambient temperatures with a differential scanning calorimeter. The heat capacity data are well behaved at T < 300 K and show a monotonic decrease in magnitude with decreasing temperature. There is no evidence for any phase transition. A standard third-law entropy value of S° = 421.7 ± 1.6 J/(mol·K) was calculated. Published experimentally based S° values for katoite are slightly lower than this value. Estimations of S° based on empirical corresponding state schemes give S° values that are much too low. This is ultimately attributed to an inability to account for the vibration behavior of the OH groups in katoite that have very weak or no H-bonding. Using this new calorimetric-based S° value and published standard enthalpy of formation data for katoite, a calorimetric-based Gibbs free energy of formation at 298 K can be obtained as ΔG°f = -5021.2 ± 16.5 kJ/mol.

Keywords : Katoite; hydrogarnet; heat capacity; standard entropy; Gibbs free energy; relaxation calorimetry; hydrous minerals; cement
Received: 2012-1-13
Accepted: 2012-3-27
Published Online: 2015-4-2
Published in Print: 2012-7-1

© 2015 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am.2012.4106
Keywords for this article
Katoite; hydrogarnet; heat capacity; standard entropy; Gibbs free energy; relaxation calorimetry; hydrous minerals; cement

Articles in the same Issue

  1. Mercury (Hg) mineral evolution: A mineralogical record of supercontinent assembly, changing ocean geochemistry, and the emerging terrestrial biosphere
  2. The 3.65 Å phase, MgSi(OH)6: Structural insights from DFT-calculations and T-dependent IR spectroscopy
  3. Vertical zonation of the Barcroft granodiorite, White Mountains, California: Implications for magmatic processes
  4. Minerals in cement chemistry: A single-crystal neutron diffraction and Raman spectroscopic study of thaumasite, Ca3Si(OH)6(CO3)(SO4)·12H2O
  5. A new high-pressure phase transition in natural Fe-bearing orthoenstatite
  6. Aluminum solubility in TiO2 rutile at high pressure and experimental evidence for a CaCl2-structured polymorph
  7. First record and timing of UHP metamorphism from zircon in the Xitieshan terrane: Implications for the evolution of the entire North Qaidam metamorphic belt
  8. Lead in zircon at the atomic scale
  9. Characterization of fluor-chlorapatites by electron probe microanalysis with a focus on time-dependent intensity variation of halogens
  10. An inversion-based self-calibration for SIMS measurements: Application to H, F, and Cl in apatite
  11. Second boiling effects on the Al-content of hornblende rims from an exhumed Cretaceous arc pluton, Stewart Island, New Zealand
  12. Heat transfer in plagioclase feldspars
  13. Transport properties and equation of state of 1-bar eutectic melt in the system CaAl2Si2O8-CaMgSi2O6 by molecular dynamics simulation
  14. High-pressure behavior of zoisite
  15. A first-principle investigation of antigorite up to 30 GPa: Structural behavior under compression
  16. Reynoldsite, Pb2Mn4+2 O5(CrO4), a new phyllomanganate-chromate from the Blue Bell claims, California and the Red Lead mine, Tasmania
  17. A new cubic perovskite in PbGeO3 at high pressures
  18. Manganoquadratite, AgMnAsS3, a new manganese-bearing sulfosalt from the Uchucchacua polymetallic deposit, Lima Department, Peru: Description and crystal structure
  19. Leucostaurite, Pb2[B5O9]Cl·0.5H2O, from the Atacama Desert: The first Pb-dominant member of the hilgardite group, and micro-determination of boron in minerals by PIGE
  20. Synthetic LiAlGe2O6: The first pyroxene with P21/n symmetry
  21. Panguite, (Ti4+,Sc,Al,Mg,Zr,Ca)1.8O3, a new ultra-refractory titania mineral from the Allende meteorite: Synchrotron micro-diffraction and EBSD
  22. Buseckite, (Fe,Zn,Mn)S, a new mineral from the Zakłodzie meteorite
  23. Experimental calibration of the effect of H2O on plagioclase crystallization in basaltic melt at 200 MPa
  24. High-pressure and high-temperature titanium solution mechanisms in silicate-saturated aqueous fluids and hydrous silicate melts
  25. Thermodynamic behavior and properties of katoite (hydrogrossular): A calorimetric study
  26. Graphite in the martian meteorite Allan Hills 84001
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