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Volume 30 Issue 5
Oct 2019
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Journal of Earth Science  > 2019  >  30(5): 964-976.
Xiang Wang, Xiaoxiang Xu, Yu Ye, Chao Wang, Dan Liu, Xiaochao Shi, Sha Wang, Xi Zhu. In-situ High-Temperature XRD and FTIR for Calcite, Dolomite and Magnesite: Anharmonic Contribution to the Thermodynamic Properties. Journal of Earth Science, 2019, 30(5): 964-976. doi: 10.1007/s12583-019-1236-7
Citation: Xiang Wang, Xiaoxiang Xu, Yu Ye, Chao Wang, Dan Liu, Xiaochao Shi, Sha Wang, Xi Zhu. In-situ High-Temperature XRD and FTIR for Calcite, Dolomite and Magnesite: Anharmonic Contribution to the Thermodynamic Properties. Journal of Earth Science, 2019, 30(5): 964-976. doi: 10.1007/s12583-019-1236-7
shu

In-situ High-Temperature XRD and FTIR for Calcite, Dolomite and Magnesite: Anharmonic Contribution to the Thermodynamic Properties

doi: 10.1007/s12583-019-1236-7
  • 1.

    State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074, China

  • 2.

    Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai 200092, China

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  • Corresponding author: Yu Ye
  • Received Date: 11 Feb 2019
  • Accepted Date: 05 Jul 2019
  • Publish Date: 01 Oct 2019
    Abstract
  • In-situ powder X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectra were measured on the natural crystals of calcite (Ca0.996Mg0.004CO3), dolomite (Ca0.497Mg0.454Fe0.046Mn0.003CO3) and magnesite (Mg0.988Ca0.010Fe0.002CO3), with a temperature up to 796 K. The thermal expansion coeffi-cients were evaluated for these carbonate minerals, resulting in the values of 2.7×10-5, 3.3×10-5 and 3.5×10-5 K-1 for calcite, dolomite and magnesite, respectively. The magnitude of these coefficients is in the same order as those for the isothermal and elastic moduli of these carbonates (e.g., calcite < dolomite < magnesite). The IR-active internal modes of the CO3 group systematically shift to lower frequencies at elevated temperature, and the isobaric (γiP) and isothermal (γiT) Grüneisen parameters for the internal modes are generally smaller than 0.5. The corresponding anharmonic parameters (ai) are typically within the range of -1.5-+1×10-5 K-1, which are significantly smaller in magnitude than those for the external modes. We also calculate the thermodynamic properties (internal energy, heat capacities and entropy) at high temperatures for these carbonates, and the anharmonic contribution to thermodynamics shows an order of calcite > dolomite > magnesite. The Debye model (harmonic approximation) would be valid for magnesite to simulating the thermodynamic properties and isotope fractionation β-factor at high P-T condition.

     

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