Reinvestigation of the System Na3AlF6-Li3AlF6

A partial phase diagram for the system Na₃AlF₆-Li₃AlF₆ was constructed from DTA and X-ray diffraction measurements. A region of solid solution extends from Na₃AlF₆ to the limiting composition Na₂LiAlF₆. At compositions between Na_1.5Li_1.5AlF₆ and NaLi₂AlF₆ a cubic phase resembling the mineral cryolithionite is stable over a narrow range of temperatures, which shifts progressively to higher temperatures with increasing lithium content. A single phase can be quenched from samples annealed within this range except near the ideal cryolithionite composition (Na_1.5Li_1.5AlF₆) where the upper temperature limit is too low to permit recombination of two solid phases to cryolithionite even with prolonged annealing. Cryolithionite precipitated from aqueous solution, a sample of the mineral, and the solid solutions containing from 53 to 65 mole % Li₃AlF₆ have identical powder patterns except for differences of lattice constants. Solid solubility of Na₃AlF₆ in Li₃AlF₆ reaches 30 mole % at the eutectic temperature.