Thermodynamic properties of ZrSiO4 zircon and reidite and of cotunnite-type ZrO2 with application to high-pressure high-temperature phase relations in ZrSiO4

Abstract

Enthalpies of high-pressure phase transitons in ZrSiO4 were measured by high-temperature drop-solution calorimetry. The enthalpies for the zircon-reidite transition in ZrSiO4 and for dissociation of reidite to cotunnite-type ZrO2 + SiO2 stishovite were obtained to be 27.5 ± 3.3 and 50.3 ± 3.0 kJ/mol, respetively, at 298 K. By thermal relaxation method, low-temperature isobaric heat capacities of ZrSiO4 reidite and cotunnite-type ZrO2 were measured, giving standard entropies at 298 K of 77.29 ± 0.04 and 49.10 ± 0.04 J/mol·K, respectively. Combining the measured enthalpies and entropies with other available thermophysical data, the transition boundaries in ZrSiO4 were calculated. The calculated zircon-reidite transiton boundary is consistent with that by in situ high-pressure expreiments by Ono et al. (2004a) within the errors. The calculated dissociation boundary of reidite has a smaller slope than that by high-pressure quench expreiments by Tange and Takahashi (2004). The equilibrium zircon-reidite transition pressure is calculated to be 8 GPa at 298 K, which is by 12–15 GPa lower than the transition pressures observed by room-temperature static compression experiments. Our results suggest that zircon transforms to reidite and dissociates into the two phases at 330 and 610 km depths, respectively, along the normal mantle geotherm. Combining the calculated phase relations with kinetics estimated from the first principles calculation may provide some insights to P, T conditions which reidites found in impact ejecta layers and craters experienced.