Thermodynamics of the System NaF-AlF3: Part V. Solid Solution in Cryolite

Electrical resistivity measurements have been used to demonstrate the existence of solid solutions of AlF₃ in the high-temperature form of cryolite above the transition at 565°C. An expression was derived for the resistivity of single-phase mixtures as a function of composition and temperature, and it was then used to deduce the composition at the solid-solid phase boundaries. At the NaF-cryolite eutectic temperature (880°C) the boundary lies at 74.8 mole pct NaF, and at the chiolite peritectic temperature (737°C) the other boundary lies at 74.4 mole pct NaF. The variation of composition with activity of NaF is reasonably consistent with the hypothesis that solid solution leads to formation of AlF ₄ ¹ ions and cation vacancies. On this basis extrapolation is made for the solid-liquid boundaries, and the solid solution region is found to touch the liquidus at 74.0 mole pct NaF. On the above hypothesis the anomalous heat content of cryolite between 888°C and the melting point can be accounted for.