Flory-Huggins' formulation, its validity and implications in retrieval of equilibrium temperature of binary and ternary systems at higher pressures, using liquid silicate data and 1 bar liquidus temperature

Abstract

For a pure phase at equilibrium with a polycomponent melt, two sets of expressions can be derived; one expressing its activity as a function of enthalpy, entropy, heat capacity and temperature, and the other by coupling a Flory-Huggins' polymerisation model with the van Laar heat of mixing term. Interaction parameters for binary and ternary systems have been computed at 1 bar by equating these two expressions. Assuming the interaction parameter to be independent of temperature, equilibrium temperatures at higher pressures can be calculated by an iterative procedure. Such retrieval calculations were carried out in simple eutectic, volatile-free systems like CaAl2Si2O8-CaMgSi2O6, Mg2SiO4-TiO2, MgSiO3-TiO2, Mg2SiO4-CaMgSi2O6, NaAlSi3O8-SiO2 and CaAl2Si2O8-CaMgSi2O6-Mg2SiO4. The close agreement between the theoretically retrieved and the experimentally determined equilibrium temperatures testifies to the validity of the model at higher pressures. The successful application of the model to simple eutectic, binary and ternary systems involving vastly dissimilar phases without imposing added constraints implies that it can be possibly extended to hitherto unknown systems provided the thermodynamic parameters of the phases involved are known.