ENTROPIES OF MIXING AND SUBSOLIDUS PHASE RELATIONS OF FORSTERITE-FAYALITE (MG2SIO4-FE2 SIO4) SOLID SOLUTION

Abstract

The heat capacities of a series of synthetic forsterite (Fo)-fayalite (Fa), Mg2SiO4-Fe2SiO4, olivines have been measured between 5 and 300 K on milligram-sized samples with the Physical Properties Measurement System (Quantum Design). The heat capacities for fayalite and fayalite-rich olivine are marked by a sharp lambda-type anomaly defining a transition from the paramagnetic to an antiferromagentic state, which in the case of fayalite occurs at TN = 64.5 K. In forsterite-rich compositions a feature in the CP data around 25 K is observable and it could possibly be linked to a magnetic transition. Additionally, all Fe-bearing olivines show a Schottky-type anomaly. Excess heat capacities of mixing, ΔCPxs, for the various Fe-Mg olivine solid-solution compositions were calculated applying the equation ΔCPxs = CPss - [(1 - XFa) CPFa + XFa CPFa] using fitted CP, polynomials for each composition. The calorimetric entropies at 298.15 K, Scal, were determined by solving the CP integral s cal,298.15 = ∫0298.15 CP/TdT. If a symmetric Margules mixing model ΔSxs = Ws·XFa(1 - XFa) is taken to describe the entropy of mixing behavior for the Fo-Fa binary, it yields an interaction parameter of Ws = -1.6 ± 1.7 J/(mol·K) on a one-cation basis. The calorimetric data thus indicate ideal entropy of mixing behavior. Adopting, however, a value of WS,Mg-FeOI = -1.6 J/(mol·K) one can calculate a value for the excess Gibbs free energy of mixing behavior. Adopting, however, a Of WG,Mg-FeOI = 6.9 kJ/mol at 1000 K using the most recent solution calorimetric study of Kojitani and Akaogi (1994) on Fo-Fa olivine with WH,Mg-FeOI = 5.3 kJ/mol. This WG,Mg-FeOI value should be considered a maximum upper limit for thermodynamic nonideality. Using solely calorimetric data, the T-X phase diagram for the Fo-Fa binary is calculated at 1 bar and 50 kbar and compared to that obtained from a model-dependent thermodynamic analysis. The results suggest that exsolution in Fe-Mg olivine should only be possible in low-temperature environments depending on kinetic behavior.