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Fe 3 O 4  has been studied by high-pressure diffraction to 43 GPa. No major changes in the spinel-type structure of magnetite is observed below 21.8 GPa. At higher pressure a sluggish transition to a highpressure modification, h-Fe 3 O 4 , is observed. The X-ray diffraction pattern of the high-pressure modification is consistent with the orthorhombic unit cell (CaMn 2 O 4 -type structure, space group Pbcm) recently proposed for h-Fe 3 O 4  by Fei et al. (1999), however, it is also consistent with a more symmetric CaTi 2 O 4 - type structure (space group Bbmm). Bulk modulus values for magnetite, K T0  = 217 (2) GPa, and h-Fe 3 O 4 , K T0  = 202 (7) GPa, are calculated from the pressure-volume data using a third-order Birch-Murnaghan equation of state. A thermodynamic analysis of the Fe-O system at high pressure is presented. The proposed equation of state of h-Fe 3 O 4  gives an increased stability of wüstite relatively to a two-phase mixture of iron and h-Fe 3 O 4  compared to earlier equations of state and removes an inconsistency in the thermodynamic description of the Fe-O system at high pressure.

Equation of state of magnetite and its high-pressure modification: Thermodynamics of the Fe-O system at high pressure