Heat capacity (C ) of rutile and α-PbO type T iO (TiO -II) were measured by the differential scanning calorimetry and P 2 2 2 thermal relaxation method. Using the results, standard entropies at 1 atm and 298.15 K of rutile and TiO -II were determined to be 50.04(4) and 46.54(2) J/mol K, respectively. Furthermore, thermal expansivity (α) determined by high-temperature X-ray diffraction measurement and mode Grüneisen parameters obtained by high-pressure Raman spectroscopy suggested the thermal Grüneisen parameter (γ ) for T iO -II of 1.7(1). By applying the obtained low-temperature C and γ , the meas- th 2 P th ured C and α data of TiO -II were extrapolated to higher temperature region using a lattice vibrational model calculation, P 2 as well as rutile. Internally consistent thermodynamic data sets of both rutile and TiO -II assessed in this study were used to thermodynamically calculate the rutile‒TiO -II phase equilibrium boundary. The most plausible boundary was obtained to be P (GPa) = 0.0074T (K) − 1.7. Our boundary suggests that the crystal growth of TiO -II observed below 5.5 GPa and 900 K in previous studies advanced in its stability field. The phase boundary calculation also suggested small, exothermic phase transition enthalpy from
Physics and Chemistry of Minerals – Springer Journals
Published: Jun 4, 2018
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