Abstract
Measurements have been made of a) the sodium content of aluminum in contact with NaF-AlF3 melts at 1020° and 1080°C, and in contact with liquid-solid mixtures along the cryolite liquidus, b) the position of the A1F3 liquidus line, and c) the electromotive force of solid-electrolyte cells with one side in the NaF-Na3AlF6 two-phase region and the other on the cryolite liquidus. With previously determined data for the activity coefficient of sodium in aluminum and for ΔH°298f for cryolite, activities of NaF and A1F3 are calculated. As a limiting condition the melts conform to a regular solution model withRTlnγ’1 = ∔12,200(1 − n’1)2 cal where γ’1=a1/n’1 and n’1 the molar fraction of either NaF or NaAlF4 calculated with them as species. This model breaks down progressively as the NaAlF4 composition is approached, the deviations starting earlier at higher temperatures. The most plausible explanation is the disproportionation equilibrium 2A1F-4 ⇌ A12F-7 + F-, stoichiometric NaAlF4 containing about 70 pct AlF- 4 at 1020° to 1080°C. The hypothetical undisproportionated NaAlF4 has a free energy of formation from NaF(I) and AlF3(s) of ΔG° = •101,235 + 32.085T + 5.929 × 107/T. This equation, together with that above for γ’NaAlF4, defines α AlF3 in all regions where the regular solution model holds. Solutions of sodium in aluminum are found to conform to Henry’s law in the range 100 to 2 ppm, contrary to recent suggestions.
Similar content being viewed by others
References
E. W. Dewing:Met. Trans., 1970, vol. 1, pp. 1691–94.
E. W. Dewing:Met. Trans., 1970, vol. 1, pp. 2211–15.
D. A. Chin and E. A. Hollingshead:J. Electrochem. Soc, 1966, vol. 113, pp. 736–39.
JANAF Thermochemical Tables: PB 168370, -1 and -2, Dow Chemical Co., Midland, Mich., 1965, 1966, and 1967.
K. Grjotheim:Contribution to the Theory of the Aluminum Electrolysis, Det Kgl Norske Videnskabers Selskabs Skrifter 1956, No. 5, Trondheim.
Anne Fenerty and E. A. Hollingshead:J. Electrochem. Soc, 1960, vol. 107, pp.993–97.
S. J. Cyvin, P. Klaboe, E. Rytter, and H. A. Øye:J. Chem. Phys., 1970, vol. 52, pp. 2776–78.
C. Solomons, J. H. R. Clarke, and J. O’M. Bockris:J. Chem. Phys., 1968, vol. 49, pp. 445–49.
J. C. Mitchell and C. S. Samis:Trans. TMS-AIME, 1969, vol. 245, pp. 1227- 34.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Dewing, E.W. Thermodynamics of the system NaF-AlF3. Part III: Activities in liquid mixtures. Metall Trans 3, 499–505 (1972). https://doi.org/10.1007/BF02642055
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF02642055