Thermodynamic properties of geikielite (MgTiO3) and ilmenite (FeTiO3) derived from vibrational methods combined with Raman and infrared spectroscopic data

Abstract

We present a model for the lattice vibrational density of states of MgTiO₃ (geikielite) and FeTiO₃ (ilmenite) that predicts thermodynamic properties, in agreement with observational data. The model is based on Kieffer’s method combined with spectroscopic data. For both substances experimental data sets are influenced by non-stoichiometry. For geikielite that affects the volume, whereas for ilmenite volume and bulk modulus are affected. We show that Kieffer’s method enables predicting bulk moduli in pressure–temperature space. We demonstrate that intrinsic anharmonicity or electronic effects significantly affect the heat capacity of ilmenite, whereas that is not the case for geikielite. We use Kieffer’s method to derive multiple-Einstein models, from which we demonstrate that thermodynamic properties are insignificantly influenced by dispersion in Grüneisen, mode-q and anharmonicity parameters for both substances. We show that our results enable predicting thermodynamic properties and shear modulus of the solid solution formed from geikielite and ilmenite. Geikielite and ilmenite are added to our thermodynamic database for the system MgO–SiO₂–FeO, to enable modeling phase stability and physical properties of titanium-rich reservoirs in the Earth’s Moon.