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Abstract: Experiments to measure the solubilities of NiO/NiAl2O4 and FeO/FeAl2O4 were performed, and the results confirmed existing literature values. The solubilities of NiAl2O4 and FeAl2O4 in Al2O3-saturated cryolite melts at 1300 K were modeled thermodynamically in terms of the Ni-containing complexes Na2NiF4 and Na4NiF6, and the Fe-containing solutes FeF2, Na2FeF4, and Na4FeF6. The experimental solubility data were fitted to multiple simultaneous equilibria. Equilibrium constants and ΔG f 0 values for the formation reactions of the these solutes were thereby estimated. The solubilities of NiO/NiAl2O4 and FeO/FeAl2O4 and solute distributions in Al2O3-undersaturated cryolite melts were calculated for a number of melt compositions from the present model. The existence of several competitive solute species is inherent to highly buffered ionic cryolite solutions where the traditional log-log methodology had previously failed to identify dominant single solutes. In such solutions, individual solutes of oxides are not likely to dominate over a wide composition range so that a more global modeling is required. The principal solute species identified in the present study exhibit reasonable three-dimensional (3-D) anion geometries.

Abstract: The experimentally well-known alumina solubility in the range of acidic to neutral cryolite-base melts has been modeled thermodynamically in terms of several oxyfluoride solutes. For an acidic melt, cryolite ratio r=1.5, the dominant solute is monoxygen Na2Al2OF6. In a less acidic regime, dioxygen Na2Al2O2F4 is dominant, whereas for neutral compositions (r=3), Na4Al2O2F6 starts to gain importance. The fit of the model to the experimental solubility data is virtually perfect. The values of the equilibrium constants for the formation of the individual solutes are reported. The formation and conversion of these oxyfluoride complexes serve as an effective buffer opposing change in the melt basicity.