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I.
INTRODUCTION
[1]
[2]
[3]
EXPERIMENTAL
solved in HCl, the resulting solution being analyzed by inductively coupled plasma (ICP).
In some selected cases, the frozen material left in the
crucible was examined microscopically and then crushed
and submitted to X-ray diffraction (XRD) analysis to identify the solid phase with which the melt had been in equilibrium.
III.
RESULTS
A. Cryoscopic Measurements
Measurements were made as described in connection
with cerium oxide.[11] In order to carry through the calculation with correction for the varying nonstoichiometry of
the solid phase separating, one must have a value for ] ln
aNaF/]NZnO. (References 9 and 10 provide details.) The value
selected is 21, which corresponds to ZnO being an inert
diluent.[12] Figure 1 shows the reduction in activity of
Na3AlF6 as a function of the ZnO added. The limiting slope
is 22, which is consistent with the dissolution process being
3ZnO 1 2AlF3 5 3ZnF2 1 Al2O3
[4]
B. Solubility Measurements
Figure 2 shows the Zn content of the melt as a function
of the alumina content. The amount of alumina generated
1100VOLUME 28B, DECEMBER 1997
[5]
mechanism and the revised activity model for cryolite-alumina melts[9] are thus mutually consistent.
From the results, the activity coefficient of ZnF2 can be
calculated. With data from Reference 13, the equilibrium
constant for Reaction [4] at 1293 K is 8.40 3 1024, the
standard state for ZnF2 being taken as the pure liquid. The
activity of AlF3 is 4.9 3 1024.[14] At the point where ZnO
and ZnAl2O4 are in equilibrium, the activity of alumina is
0.0336 (as discussed previously), so the activity of ZnF2 is
1.8 3 1023. The concentration of Zn in solution is about
1.6 wt pct. This is a molar fraction of ZnF2 of 0.013 (based
on NaF, AlF3, and ZnF2 as constituents) and gives an activity coefficient of 0.14.
ACKNOWLEDGMENTS
Fig. 3Phase diagram ZnO-cryolite.
REFERENCES
DISCUSSION
[6]