Analbite - Sanidine Thermodynamic Mixing Properties: Highly Precise HF Solution Calorimetric Data Across A Twenty-Member Crystalline Solution Series

Enthalpies of K-Na mixing for the analbite - sanidine feldspar series were investigated by Hovis (1988, J. Petrology) in the early 80's. That work was based on data at a limited number of compositions, owing to the large sample sizes required for HF solution calorimetric measurements at the time. Thermodynamic mixing properties for mineral series, especially those exhibiting compositionally asymmetric mixing quantities, are best defined when samples at a large number of compositions are utilized. Enabled by the small sample sizes now possible for HF solution calorimetric dissolutions (Hovis et al., 1998, Amer. Mineral.), we revisit feldspar thermodynamic properties, having synthesized an analbite - sanidine series consisting of samples at 20 compositions. Solution calorimetric experiments on these samples at 50 °C in 20.1 wt% HF under isoperibolic conditions have resulted in highly precise calorimetric data (standard deviation per sample averaging 0.06 % of the heat of solution). Although enthalpies of K-Na mixing based on the new data display some degree of compositional asymmetry, with a maximum value of 4.8 kJ/mol at a mole fraction potassium of 0.47, the distribution of enthalpy-of-mixing values remains nearly symmetric with respect to K content. This contrasts significantly with data for Al-Si ordered low albite - microcline crystalline solutions, reinvestigated via synthesis of a 21-member series, which show significantly higher mixing magnitudes and considerably greater asymmetry with respect to composition. The maximization of enthalpies of K-Na mixing at sodic compositions correlates well with the sodic critical compositions for both solvi. The lower mixing magnitudes for analbite - sanidine are consistent with the comparatively lower critical temperature of the analbite - sanidine solvus (e.g., Smith & Parsons, 1974, Mineral. Mag.) relative to that for low albite - microcline (Bachinski & Müller, 1971, J. Petrology). Entropies of K-Na mixing for analbite - sanidine have been calculated by combining present enthalpy data with Gibbs free energies of mixing derived from the earlier phase equilibrium study of Hovis et al. (1991, Amer. Mineral.). These may be compared with directly measured entropy data for analbite - sanidine based on the heat capacity measurements of Haselton et al. (1983, Amer. Mineral.). Thanks to the National Science Foundation for funding this research.