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The Solubility of ZnO and ZnAl2O4 in Cryolite Melts

E.W. DEWING, S. ROLSETH, L. STEN, and J. THONSTAD


The solubilities of ZnO and ZnAl2O4 in cryolite-alumina melts at 1020 7C have been measured.
ZnAl2O4 is the stable solid phase at Al2O3 contents greater than 1.45 5 0.2 wt pct. The results can
be represented (in terms of wt pct Zn in solution and in the range 1.2 to 13.6 pct Al2O3) by
log (pct Zn) 5 0.491 1 1.90 log (pct Al2O3)
where (pct Al2O3) includes the alumina formed by the dissolution reaction. The results are discussed
in terms of the variation of the activity of alumina with its concentration and are consistent with the
dissolution mechanism:
3ZnO 1 2AlF3 5 3ZnF2 1 Al2O3
The activity coefficient of ZnF2 in dilute solution with respect to a pure liquid standard state is 0.14.

I.

INTRODUCTION

THE search for materials with which nonconsumable


anodes for aluminum production might be constructed has
led to renewed interest in the solubilities of metal oxides
in cryolite melts. Zinc oxide is well known as an electronic
conductor, at least when it is in a slightly reduced form,
and its solubility, together with the solubility of the associated zinc aluminate, ZnAl2O4, is the subject of this work.
Existing literature data are unsatisfactory. Chasanov[1] reported a solubility of 0.75 wt pct and Belyaev et al.[2] one
of 0.51 wt pct, both at 1000 7C. It must be noted, however,
that pure cryolite melts at 1011 7C,[3] and those quantities
of ZnO are quite insufficient to lower the melting point to
1000 7C. One therefore suspects that the cryolite was impure, and, if one of the impurities was alumina, it is known
to have a drastic effect since Belyaev et al.[2] also reported
a solubility of 0.004 wt pct in the presence of 5 wt pct
Al2O3. Hayakawa and Kido[4] determined the phase diagram
and reported a eutectic solubility of about 2.5 wt pct at 975
7C, but they too gave the melting point of cryolite as 1000
7C, and the slope of their liquidus is much steeper than can
be accounted for by a normal cryoscopic calculation.
Rolin and Bernard[5] used a visual technique to determine
solubility and reported 0.53 wt pct at 1030 7C.
None of these authors made any mention of the existence
of the zinc aluminate spinel, ZnAl2O4.
The Gibbs free energy of the reaction
ZnO (s) 1 Al2O3 (a) 5 ZnAl2O4 (s)

[1]

has been determined by Jacobs[6] in the region of 700 7C


to 900 7C as
DG7 5 210,750 1 1.57 T 5 150 cal

[2]

The enthalpy term is in virtually perfect accord with the

ERNEST W. DEWING, 648, Pimlico Pl., Kingston, ON, Canada K7M


5T8, is retired. S. ROLSETH, Scientist, and L. STEN, Technician, The
Foundation for Scientific and Industrial Research, and J. THONSTAD,
Professor of Electrochemistry, Institute for Industrial Electrochemistry, are
with the Norwegian University of Science and Technology, 7034
Trondheim, Norway.
Manuscript submitted June 14, 1996.
METALLURGICAL AND MATERIALS TRANSACTIONS B

calorimetric value of 210,560 5 300 cal from Navrotsky


and Kleppa.[7] Thus, at 1020 7C (1293 K),
aZnO z aAl2O3 5 0.0336

[3]

in equilibrium with the aluminate.


On the basis of an existing[8] relation between alumina
activity and concentration, it was predicted that an activity
of 0.0336 would occur at 4.0 wt pct Al2O3, so that ZnO
was expected to be stable at Al2O3 contents below that, and
ZnAl2O4 above. The prediction has proved impossible to
reconcile with the results subsequently described, and that
has led to a reassessment of activities in the binary
Al2O3-Na3AlF6 system.[9]
Information on the chemical state of the dissolved material in dilute solutions can be obtained from cryoscopic
measurements, but the reassessment of the Al2O3-Na3AlF6
system[9] has shown the necessity to allow for the fact that
solid cryolite melts incongruently;[10] that has been done
here. For more concentrated solutions, the variation of solubility with the alumina content of the melt is a prime diagnostic tool. In general, as the alumina content goes up,
the solubility of any other oxide may be expected to go
down due to the common ion effect. A detailed treatment
is given in Section IV.
II.

EXPERIMENTAL

Cryolite-alumina melts ('130 g) were made up by


weight from handpicked Greenland cryolite and were contained in a platinum crucible. ZnO or ZnAl2O4 (3 to 5 g)
was added as pieces of dense, sintered material. The standard experimental temperature was 1020 7C. Oxygen was
bubbled through the melt via a platinum tube for either 3
or 5 hours to provide stirring, and then bubbling was
stopped for 30 minutes to allow any solid material in suspension to settle to the bottom. The melt was sampled by
dipping a cold silica tube into it so that the liquid froze
onto the tube. Samples were analyzed by X-ray fluorescence (XRF), either by Alcan International Ltd. (Jonquie`re,
PQ, Canada) or by Ljunga Lab AB (Ljungaverk, Sweden),
or the fluoride materials were dissolved in a 30 wt pct AlCl3
z 6H2O solution and the insoluble oxide subsequently disVOLUME 28B, DECEMBER 19971099

Fig. 1Cryoscopic results. The reduction of cryolite activity (d aCr) is


shown as a function of the molar fraction of ZnO.

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]

since Al2O3 itself is known to dissociate to three particles


in dilute solution so that three ZnOs produce a total of six
foreign particles.
[9]

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

Fig. 2Solubility of ZnO as a function of total alumina content (log-log


scale). (The alumina formed by the dissolution reaction is included.) The
information at the bottom left of the diagram gives the starting material,
the time of equilibration, and the method of analysis.

by the dissolution reaction (Reaction [4], or the analogous


reaction with ZnO z Al2O3) has been added to the weighedin amount, and the Greenland cryolite used has been assumed to contain 0.3 wt pct Al2O3. The following should
be noted: (a) there is no significant difference between samples equilibrated for 5 hours and those equilibrated for 3
hours; and (b) there is no significant difference between
ICP and XRF analyses, although the former are certainly
more precise, especially in the lower ranges. At levels less
than about 0.1 pct Zn, XRF analyses were essentially
worthless.
The line in Figure 2 (based on the ICP analyses only) is
log (wt pct Zn) 5 0.491 2 1.90 log (wt pct Al2O3)

[5]

The statistical standard error of the slope is 50.11, and the


standard deviation is 50.14.
Three samples of the frozen material remaining, in the
crucible were examined microscopically and by XRD. Only
when no alumina had been added was the lump of ZnO put
in initially still there, apparently unchanged. With allowance for the alumina formed by the dissolution reaction and
the 0.3 pct assumed present in the Greenland cryolite, the
final alumina content would be 1.24 pct. With 0.5 wt pct
Al2O3 added, the lump had disintegrated, and XRD analysis
showed peaks of both ZnO and ZnAl2O4. The final alumina
content would be 1.62 pct minus an unknown amount
which had precipitated as ZnAl2O4. One can thus assign the
alumina concentration at which ZnO and ZnAl2O4 are in
METALLURGICAL AND MATERIALS TRANSACTIONS B

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.

equilibrium as 1.45 5 0.2 wt pct Al2O3. With 3.0 pct added


Al2O3, only ZnAl2O4 was detected.
IV.

REFERENCES

DISCUSSION

The phase diagram for ZnO-Na3AlF6 is shown as Figure


3. (The melting point of pure cryolite has been taken as
1011 7C, and the melting points of individual batches have
been corrected to it.) The eutectic lies at 2.9 pct ZnO and
994 7C. That is a higher solubility than measured at 1020
7C (the points at the top of the line in Figure 2 are those
in which no alumina was added).
Where ZnAl2O4 is the stable solid phase, the dissolution
reaction is
3ZnAl2O4 1 2AlF3 5 3ZnF2 1 4Al2O3

[6]

The activities of ZnAl2O4 and AlF3 are constant, so that


aZnF2 is proportional to (aAl2O3)24/3. If the activity coefficient
of ZnF2 is constant (a plausible assumption since the concentrations are low), and the activity of alumina is proportional to its concentration to the power 1.5 (which is the
case in concentrated solutions[9]), then a slope of 22 is predicted for the line in Figure 2. The observed slope of 21.9
5 0.1 is in satisfactory agreement. The proposed solution

METALLURGICAL AND MATERIALS TRANSACTIONS B

We are indebted to Thorild Eggen for performing the ICP


analyses and to Tharald Tharaldsen for the XRD patterns.
Thanks are expressed to Permascand AB (now Akzo Nobel) for financial support and to Permascand and Moltech
s.a. for permission to publish the results.

1. E.I. Chasanov: Legk. Metall., 1936, vol. 12, pp. 16-21.


2. A.I. Belyaev, M.B. Rapoport, and L.A. Firsanova: Metallurgie des
Aluminiums, VEB Verlag Technik, Berlin, 1956, p. 74.
. Sterten, and T.
3. A. Solheim, S. Rolseth, E. Skybakmoen, L. Sten, A
Stre: in Light Metals 1995, J.E. Evans, ed., TMS, Warrendale, PA,
pp. 451-60.
4. Y. Hayakawa and H. Kido: J. Electrochem. Soc. Jpn., 1952, vol. 20,
pp. 263-65.
5. M. Rolin and M. Bernard: Bull. Soc. Chim. France, 1963, pp. 103538.
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pp. 479-98.
8. E.W. Dewing: Can. Met. Q., 1991, vol. 30, pp. 155-61.
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28B, pp. 1089-93.
10. E.W. Dewing: Metall. Mater. Trans. B, 1997, vol. 28B, pp. 1095-97.
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N. Aalberg: Metall. Mater. Trans. B, 1995, vol. 26B, pp. 81-86.
12. E.W. Dewing: Metall. Trans. B, 1989, vol. 20B, pp. 675-77.
13. Thermochemical Properties of Inorganic Substances, 2nd ed., O.
Knacke, O. Kubaschewski, and K. Hesselmann, eds., Springer-Verlag,
Berlin, 1991.
14. E.W. Dewing: Metall. Trans. B, 1990, vol. 21B, pp. 285-94.

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