An internally consistent thermodynamic data set for phases of petrological interest

Abstract

The thermodynamic properties of 154 mineral end-members, 13 silicate liquid end-members and 22 aqueous fluid species are presented in a revised and updated data set. The use of a temperature-dependent thermal expansion and bulk modulus, and the use of high-pressure equations of state for solids and fluids, allows calculation of mineral-fluid equilibria to 100 kbar pressure or higher. A pressure-dependent Landau model for order-disorder permits extension of disordering transitions to high pressures, and, in particular, allows the alpha-beta quartz transition to be handled more satisfactorily. Several melt end- members have been included to enable calculation of simple phase equilibria and as a first stage in developing melt mixing models in NCKFMASH. The simple aqueous species density model has been extended to enable speciation calculations and mineral solubility determination involving minerals and aqueous species at high temperatures and pressures. The data set has also been improved by incorporation of many new phase equilibrium constraints, calorimetric studies and new measurements of molar volume, thermal expansion and compressibility. This has led to a significant improvement in the level of agreement with the available experimental phase equilibria, and to greater flexibility in calculation of complex mineral equilibria. It is also shown that there is very good agreement between the data set and the most recent available calorimetric data. kinetics which apply to determining directly the greatest majority of such equilibria in the laboratory, for forming solid solutions, and inclusion of aqueous and silicate melt species), and provides uncertainties especially at lower temperatures, as well as the diYculty of establishing reversals of reactions involving solid allowing the likely uncertainties on the results of thermodynamic calculations to be estimated. This is a solutions. The levels of precision and accuracy required of thermodynamic data in order to be able to forward- critical issue in that calculations using data sets should always involve uncertainty propagation to help evalu- model synthetic and natural mineral assemblages mean that the continuing upgrading and expansion of the ate the results. Because the experimental phase equilib- ria involve overlapping subsets of compositional space, data set by incorporation of new phase equilibrium constraints, calorimetry and new measurements of the derived thermodynamic data are highly correlated, and it is only the inclusion of the correlations which molar volume, thermal expansion and compressibility are more than justified. enables the reliable calculation of uncertainties on mineral reactions to be performed. Earlier work on mineral thermodynamic data sets for rock-forming minerals includes compilations of The thermodynamic data extraction involves using weighted least squares on the diVerent types of data