Calorimetric investigation of Na-K mixing and polymorphism in the alkali feldspars

Abstract

Heat of solution measurements of the enthalpies of Na-K mixing, Al-Si ordering, and fusion for crystalline solutions and end-member phases in the system Na(AlSi 3 O 8 )–K(AlSi 3 O 8 ) were obtained with a vacuum-jacketed, isoperibolic calorimeter using 20.1 percent hydrofluoric acid at temperatures ranging from 40 to 60°C. Heat of solution data for artificially prepared microcline (–low-albite) crystalline solutions at 49.7°C are represented by Δ H sol = −149.408 + 5.230 N 2 − 5.928 N 1 N 2 2 − 8.457 N 2 N 1 2 kcal/mole based on 39 measurements of 14 different bulk compositions, where N 1 and N 2 denote the mole fractions of NaAlSi 3 O 8 and KAlSi 3 O 8 respectively. The thermochemical uncertainty of the above least-squares formulation is ± 0.032 kcal/mole. Unit-cell parameters determined by least-squares refinement of diffraction data indicate that the excess volumes of Na-K mixing of these microcline solutions are positive over the entire composition range. Combining the calorimetric and crystallographic data leads to the following expression for the variation of molar enthalpy of mixing with pressure: Δ H ex = (5928 + 0.110 P) N 1 N 2 2 + (8457 + 0.110 P ) N 2 N 1 2 cal/mole. The sign and magnitude of Δ H ex determined by calorimetry agree closely with Δ H ex calculated from a third-order Margules formulation of high-temperature two-phase equilibrium data in the critical region.