X-ray diffraction study of magnesite at high pressure and high temperature

Abstract

P–V–T measurements on magnesite MgCO3 have been carried out at high pressure and high temperature up to 8.6 GPa and 1285 K, using a DIA-type, cubic-anvil apparatus (SAM-85) in conjunction with in situ synchrotron X-ray powder diffraction. Precise volumes are obtained by the use of data collected above 873 K on heating and in the entire cooling cycle to minimize non-hydrostatic stress. From these data, the equation-of-state parameters are derived from various approaches based on the Birch-Murnaghan equation of state and on the relevant thermodynamic relations. With K′0 fixed at 4, we obtain K0=103(1) GPa, α(K−1)=3.15(17)×10−5 +2.32(28)×10−8 T, (∂KT/∂T)P=−0.021(2) GPaK−1, (dα/∂P)T=−1.81×10−6 GPa−1K−1 and (∂KT/∂T)V= −0.007(1) GPaK−1; whereas the third-order Birch-Murnaghan equation of state with K′0 as an adjustable parameter yields the following values: K0=108(3) GPa, K′0=2.33(94), α(K−1)=3.08(16)×10−5+2.05(27) ×10−8 T, (∂KT/∂T)P=−0.017(1) GPaK−1, (dα/∂P)T= −1.41×10−6 GPa−1K−1 and (∂KT/∂T)V=−0.008(1) GPaK−1. Within the investigated P–T range, thermal pressure for magnesite increases linearly with temperature and is pressure (or volume) dependent. The present measurements of room-temperature bulk modulus, of its pressure derivative, and of the extrapolated zero-pressure volumes at high temperatures, are in agreement with previous single-crystal study and ultrasonic measurements, whereas (∂KT/∂T)P, (∂α/∂P)T and (∂KT/∂T)V are determined for the first time in this compound. Using this new equation of state, thermodynamic calculations for the reactions (1) magnesite=periclase+CO2 and (2) magnesite+enstatite=forsterite+CO2 are consistent with existing experimental phase equilibrium data.