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Heat capacity, entropy, and phase equilibria of dmitryivanovite

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Abstract

The heat capacity (C p ) of dmitryivanovite synthesized with a cubic press was measured in the temperature range of 5–664 K using the heat capacity option of a physical properties measurement system and a differential scanning calorimeter. The entropy of dmitryivanovite at standard temperature and pressure (STP) was calculated to be 110.1 ± 1.6 J mol−1 K−1 from the measured C p data. With the help of new phase equilibrium experiments done at 1.5 GPa, the phase transition boundary between krotite and dmitryivanovite was best represented by the equation: P (GPa) = −2.1825 + 0.0025 T (K). From the temperature intercept of this phase boundary and other available thermodynamic data for krotite and dmitryivanovite, the enthalpy of formation and Gibbs free energy of formation of dmitryivanovite at STP were calculated to be −2326.7 ± 2.1 and −2,208.1 ± 2.1 kJ mol−1, respectively. It is also inferred that dmitryivanovite is the stable CaAl2O4 phase at STP and has a wide stability field at high pressures whereas the stability field of krotite is located at high temperatures and relatively low pressures. This conclusion is consistent with natural occurrences (in Ca–Al-rich inclusions) of dmitryivanovite and krotite, where the former is interpreted as the shock metamorphic product of originally present krotite.

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Acknowledgments

The authors gratefully acknowledge the constructive reviews of H Long, which improved the quality of the manuscript. This work was supported by an NSERC Discovery Grant to R. A. Secco, NASA grant NNX11AG64G to A. C. Withers, and grants P21370-N21 and P23056-N21 of the Austrian Science Fund (FWF) to E. Dachs and A. Benisek.

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  1. Department of Earth Sciences, University of Western Ontario, London, ON, N6A 5B7, Canada

    Wenjun Yong & Richard A. Secco

  2. Fachbereich Materialforschung & Physik, Abteilung Mineralogie, Universität Salzburg, Hellbrunnerstrasse 34, 5020, Salzburg, Austria

    Edgar Dachs & Artur Benisek

  3. Department of Earth Sciences, University of Minnesota, Minneapolis, MN, 55455, USA

    Anthony C. Withers

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  1. Wenjun Yong
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Correspondence to Wenjun Yong.

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Yong, W., Dachs, E., Benisek, A. et al. Heat capacity, entropy, and phase equilibria of dmitryivanovite. Phys Chem Minerals 39, 259–267 (2012). https://doi.org/10.1007/s00269-012-0481-4

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