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The Content of Sodium in Aluminum in Laboratory and in Industrial Cells

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 THE CONTENT OF SODIUM IN ALUMINIUM IN LABORATORY AND IN INDUSTRIAL CELLS

J. Thonstad1), S. Rolseth1), J. Rødseth2), O. Lund2), J. Tonheim2), V. Danielik3), P. Fellner3) and J. Híveš3)

1)
Department of Materials Technology and Electrochemistry, Norwegian University of Science and Technology,
7491 Trondheim, Norway
2)
Hydro Aluminium Karmøy, 4265 Håvik, Norway
3)
Department of Inorganic Technology, Slovak University of Technology in Bratislava, 81237 Bratislava, Slovakia

Abstract 0.99). As a result of the ionic migration and the electrochemical

reaction, concentration gradients of the species taking part in these
The concentration of sodium in molten aluminium in contact with processes arise at the metal/electrolyte interface. The situation is
cryolite-based melts is determined by the equilibrium illustrated schematically in Fig. 1. The steepness of the
3 NaF + Al = 3 Nain Al + AlF3. concentration gradients is influenced by the cathodic current
Laboratory data for varying electrolyte composition and density, fluid dynamic forces (magnetics, gas evolution, thermal
temperature are compared with a thermodynamic model. During gradients), and by convection caused by gradients in interfacial
electrolysis the content of sodium increases with increasing tension (the so-called Marangoni effect).
current density, caused by a concentration gradient at the cathode,
which gives rise to concentration overvoltage. On the assumption
of equilibrium between the electrolyte adjacent to the cathode and
the aluminium, the composition of the electrolyte at the interface
can be estimated. A new metal sampling technique for industrial Concentration
cells was introduced to prevent sodium losses during sampling.
The content of sodium varied with the alumina feeding cycle, and NaF
it decreased with increasing temperature and with decreasing
aluminium fluoride. These trends, which apparently are in conflict
with thermodynamic data, will be discussed.
AlF3
Introducrion

Sodium and calcium are always present as undesired impurities in
aluminium produced by the Hall-Héroult process [1]. When
lithium fluoride and magnesium fluoride are added to the cryolite-
alumina-based electrolyte, the metal will also contain these
metals, due to exchange equilibria of the type,
MF + 1/3 Al = M(in Al) + 1/3 AlF3 M = Li, Na
MeF2 + 2/3 Al = Me(in Al) + 2/3 AlF3 Me = Ca, Mg
A thermodynamic treatment of these equilibria is presented in the
Appendix. When molten aluminium is polarized, the content of
sodium in the aluminium increases, and we observe a cathodic
overvoltage, which is mainly a concentration overvoltage [1]. The
primary cathode reaction is the reduction of Al(III) species, and it
can be written schematically as follows,
AlF3 + 3Na+ + 3e-= Al + 3NaF
The electrical charge is transported mainly by Na+ cations (tNa+ =
Boundary layer Bulk electrolyte
Distance from Al cathode
Figure 1: Concentration gradients at the metal / electrolyte
(1) interface.
(2)
Keller et al. [2] made estimates of the mass transfer coefficient for
the transfer of Al(III) species through the boundary layer. The
composition of the melt at the interface and the sodium content in
the metal could then be derived. By varying the mass transfer
coefficient from 10×10-3 cm s-1 to 1×10-3 cm s-1 the sodium
content varied from 46 ppm to 110 ppm at 0.5 A cm-2 cathodic
current density for an electrolyte with NaF/AlF3 molar ratio CR =
2.3 and 950 ºC.
(3) Tabereaux [3] showed that the average sodium level in the
aluminium in industrial cells depends on cell technology. Older
technology with less stable magnetics shows lower sodium

J.Thonstad et al. 1 of 7
contents than modern cells with well-balanced magnetic fields. As
an example, Soderberg cells can average about 70 ppm Na, while
modern prebakes can average 150 ppm. However, it can be a wide
variation around these avarages. Modern stable cells also achieve
higher current efficiency, so Tabereaux concluded that there in an
indirect correlation between high current efficiency and high
sodium contents.
Investigations of the content of sodium in aluminium and of the
cathodic overvoltage, are much easier to perform in the laboratory
than in industrial cells. Results obtained in laboratory cells are
helpful in understanding the behaviour in industrial cells. In the
present paper we will present both laboratory and industrial data
on the content of sodium in polarized aluminium. Cathodic
overvoltage data obtained in the laboratory will be correlated with
the contents of sodium in the aluminium, and sodium contents in
industrial cells will be related to operational parameters.
Results and discussion
Equilibrium data The contents of alkali and alkaline earth metals
in aluminium in equilibrium with cryolite melts have been
investigated by several authors [1, 5 - 12]. Tingle et al. [5] studied
how the content of sodium in aluminium in equilibrium with NaF
– AlF3 melts varied with time, concentration and temperature.
Dewing and van der Kouwe [6, 7] derived a regression equation
for the contents of sodium and magnesium in aluminium in
equilibrium with cryolite-based melts. Peterson and Tabereaux [8]
published a regression equation for the contents of sodium,
calcium and magnesium in aluminium in equilibrium with
cryolite-based melts at 970 °C.

Laboratory Studies

Experimental

Analytical grade chemicals were used (Lachema, Brno) to prepare

the melts. Aluminium fluoride was sublimed from commercial
grade AlF3; the aluminium was of 99.999 % purity. A
homogenized mixture of Na3AlF6 + AlF3 + CaF2 + Al2O3 (90 g)
together with 50 g of aluminium was weighed into a graphite
crucible with sintered alumina, and the melt was saturated with
alumina (Al2O3(sat)). When the melt was not saturated with
alumina, thin-walled pyrolytic boron nitride (BN) crucibles
(Ø = 26 mm, h = 40 mm) were used. The alumina content in
saturated melts can be calculated according to the equation given
by Skybakmoen et al. [4]. The crucible was placed in a furnace
preheated to a chosen temperature. After melting, the sample was
kept for another 30 min at that temperature. When equilibrium
was achieved, 0.8 g of metal was siphoned from the alumina
crucible into a quartz tube (inner diameter 4 mm) by means of a
syringe. The sample was quenched in water mixed with ice.

When BN crucibles were used, they were removed from the

furnace and cooled in a flow of argon. The cooled metal sample
was cleaned mechanically, dissolved in HCl (diluted to 1:1) and
analyzed. The content of sodium was determined by atomic
absorption spectroscopy. The standard deviation of the sodium
analysis depended on the concentration, being about 5% of the
content of Na. This deviation significantly exceeds the analytical
error, so it is probably affected by loss of sodium from the sample
during solidification.
In addition to the equilibrium studies in the absence of
electrolysis, the cathodic overvoltage was investigated as a
function of current density, melt composition and temperature. A
laboratory cell similar to that used in the study of the equilibrium
sodium content was used as depicted in Fig. 2. Dissolution of the
corundum lining kept the concentration of alumina near
saturation, making it possible to conduct electrolysis for several
hours without feeding alumina.
The cathodic overvoltage was determined by a method based on
fast current interruption (~50 ns). The potential decay of the
cathode voltage was monitored on an oscilloscope. Extrapolation
of the transient curves to zero time yielded the IR-free cathode
potential, referred to the aluminium reference electrode.
Figure 2: The experimental cell for polarization studies. 1 - anode
current lead, 2 - alumina tube, 3 - alumina lining, 4 - graphite
crucible, 5 - graphite anode, 6 - Al reference electrode, 7 - Al
cathode, 8 - Mo plate, 9 - crucible supporter, 10 - cathode current
lead.
The literature data are compared with the present results in Fig. 3.
The curves in the figure correspond to the content of sodium
calculated according to a thermodynamic model (see Appendix).
From Figs. 3 and 4 it can be seen that alumina and calcium
fluoride have a minor influence on the content of sodium. This is
an important conclusion because the content of alumina varies
during electrolysis.
Polarisation data During electrolysis the content of sodium in
aluminium is closely related to the cathodic concentration
overvoltage. Fig. 5 shows how the content of sodium and the
cathodic overvoltage varied with time, measured at two current
densities, as specified in the legend. The true cathodic current
densities were estimated on the basis of a numerical simulation of
the current distribution in the cell [13]. The cathodic overvoltage,
as well as the content of sodium in aluminium, reached a constant

J.Thonstad et al. 2 of 7
value after 10 - 15 minutes of electrolysis. The results were found
to be reproducible. 110 350

100 300

300 90 250

w (Na) / ppm
80 200

- ηC / mV
w(Na) / ppm

70 150
200

60 100

50 50
100

40 0
0 5 10 15 20 25 30 35
time / min
0
1.5 2.0 2.5 3.0 3.5
CR Figure 5: The time dependence of the cathodic overvoltage at two
current densities (jc), and the time dependence of the content of
sodium in polarized aluminium. Na3AlF6 + 10 wt. % AlF3,
Figure 3: The equilibrium content of sodium in aluminium (CR = Al2O3(sat), 1000 ºC. ○ – jc = 0.375 A cm-2, □ – jc = 0.250 A cm-2,
nNaF / nAlF3). ○ - this work, Al2O3(sat), 1000 °C, ● - this work, ■ – the concentration of sodium at jc = 0.250 A cm-2.
alumina-free melt, 1000 °C, ◊ - Tingle et al. [5], 1000 °C, ∆ -
Fellner and Lubyová [9], 1000 °C. Full line - calculated for
alumina-free melt, 1000 °C. Dashed line - calculated for 1/3 AlF3 (II) + NaF(I) = 1/3 AlF3(I) + NaF(II) (5)
Al2O3(sat) melt; 1000 °C. Dotted line - calculated for alumina-free
melt; 950 °C. where (I) and (II) represent the compositions at the interface and
in the bulk, respectively. The cell potential when the two
300
compartments have different concentrations, can be expressed as,

RT  a ( AlF3 , I )   a ( NaF , II ) 

250 1/ 3
(6)
E= ln  
 a ( AlF3 , II )   a ( NaF , I ) 
200 F
  
CR=3
w(Na) / ppm

150
where a(i) are the activities. A cathodic overvoltage is always
negative. This also follows from the shift in the concentrations of
50 CR = 2 NaF and AlF3 (see Fig. 1).
The chemical reaction at the cathode surface determining the
equilibrium sodium content, can be written as,

0 1/3 Al(l) + NaF(melt) = 1/3 AlF3(melt) + Na (in Al) (7)

0 2 4 6 8 10
or
w(CaF2) / wt. % Al(l) + 4 NaF(melt) = 3 Na(in Al) + NaAlF4 (melt) (8)

Figure 4: The influence of calcium fluoride on the content of
sodium in aluminium. □ - data at 1030 °C, CR = 3, Al2O3(sat); ■ -
data at 970°C, CR = 3, Al2O3(sat); ○ - data at 970 °C, CR=2,
Al2O3(sat); ● - data at 970 °C, CR = 2, alumina-free melt; full
lines - calculated according to the thermodynamic model.
The two reaction schemes are equivalent. The thermodynamics of
these reactions is discussed in the Appendix. Owing to these
equilibria, the potential of the concentration cell and hence the
cathodic overvoltage, η, can be expressed as a function of the
activity of sodium in aluminium, as follows,

A theoretical calculation of the cathodic overvoltage was based on RT  c ( Na , j = 0 )  (9)

the assumption that thermodynamic equilibrium is always
established between the electrolyte adjacent to the cathode and the
molten aluminium cathode. The composition at the interface can
then be estimated from the content of sodium in the polarized
aluminium.
In accordance with literature [1] it was assumed that the cathodic
concentration overvoltage equals the emf of the following
concentration cell:
Al | NaF(I), AlF3(I) || NaF(II), AlF3(II) | Al
with the cell reaction,
η= ln  
F  c ( Na , j ) 
where c(Na, j) denotes the concentration of sodium in polarized
aluminium and c(Na, j = 0) is the equilibrium concentration of
sodium at zero current density. It is assumed that Henry`s law
applies for sodium in aluminium.
It is known [14, 15] that the cathodic overvoltage depends
strongly on the fluid dynamics at the aluminium/melt interface
(4) and thus also on the design of the cell. But because we used the
same cell for both studies, we can compare these two sets of data,
using Eq. (9).

J.Thonstad et al. 3 of 7
Fig. 6 shows semi-logarithmic plots of the cathodic overvoltage as solidifies very rapidly. The sampler is then removed from the cell;
a function of current density for melts having different excess the body (heat treated resin sand) is crushed and the aluminium
contents of AlF3 (10 and 20 wt. %, respectively) and containing 0 disk (12×35 mm, 31 g) can be removed.
or 5 wt. % CaF2. It can be seen that the addition of calcium
fluoride has only a minor influence on the cathodic overvoltage, 5.4
which is in agreement with the equilibrium studies. The lines in 5.3
Fig. 6 correspond to overvoltages calculated according to Eq. (9).
5.2
The data on the content of sodium in polarized aluminium were
taken from previous mesurements in the same cell [10-12]. 5.1
5.0
200 4.9

ln(ηC/mV)
4.8
180
4.7
160
4.6
140 4.5
-ηC / mV

120 4.4

100
4.3
4.2
80 7.70 7.75 7.80 7.85 7.90 7.95 8.00 8.05 8.10 8.15
-4
60
1/(T/K).10

40
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 Figure 7: Cathodic overvoltage versus the inverse temperature for
j / A.cm-2 three current densities. Na3AlF6 + 10 wt. % AlF3 + 5 wt. % CaF2
+ Al2O3(sat). ∇ - jC = 0.75 A cm-2; * - jC = 0.50 A cm-2; □ - jC =
0.25 A cm-2. Full lines – calculated from Arrhenius plots.
Figure 6: The cathodic overvoltage vs. current density (semi-
logarithmic scale) obtained in cryolite-based melts, Al2O3(sat) at
1000 ºC. □ - Na3AlF6 + 10 wt. % AlF3; ∇ - Na3AlF6 + 10 wt. %
AlF3 + 5 wt. % CaF2; ○ - Na3AlF6 + 20 wt. % AlF3; full lines –
calculated; dotted lines - extrapolation of the full line.

In Fig. 7, the cathodic overvoltage obtained in a Na3AlF6 +

12 wt. % AlF3 + 5 wt. % CaF2 + Al2O3 (sat) melt, are plotted as
a function of the inverse temperature. The cathodic overvoltage
increased markedly with decreasing temperature. The data was
described by an Arrhenius plot,

ln η = A + B / T (10)

where T is the temperature in Kelvin. The parameter B equals

11 600. The fit of the experimental data to the Arrhenius equation
is demonstrated by the full lines in Fig. 7.

Measurements in industrial cells

Sampling

The common way of sampling metal from aluminium cells is to

take a sample in a ladle, skim off the accompanying bath and pour
the metal into a steel mold. This procedure leads to appreciable
losses of sodium due to evaporation and air oxidation. The boiling
point of sodium is as low as 883 ºC, and upon solidification of the Figure 8: The Electro-Nite SA-E122 sampler.
aluminium, a liquid sodium phase separates out (M.p. 95 ºC).
To avoid losses of sodium, rapid quenching of the metal is A regression analysis was made on a large number of analytical
essential. Several homemade devices were tested, but it was found data, where conventional sampling with a ladle and the Electro-
that a commercially available sampler (Heraeus Electro-Nite SA- Nite sampler were compared. The following relationship was
E122) gave the best results. It is simple to use and gives quite found:
reproducible results (± 5 %) for sodium analyzed on a normal
emission spectrograph. A photo of the sampler is shown in Fig. 8. Na(Electro-Nite) = 1.3 (ladle) + 40 (11)
It is attached to a cardboard rod and dipped into the metal,
whereby aluminium flows in between two steel plates and

J.Thonstad et al. 4 of 7
This equation shows that more than 30 % of the sodium was lost
during sampling by the conventional procedure. In the following
all results reported are taken with the Electro-Nite sampler (with
the exception of Fig. 9a).
Results
Tests were made on 84 kA Soderberg cells, one cell-line of
modernized 160 kA prebake cells and one modern 180 kA
prebake (AP18) cell-line. Typical sodium levels were 60-100 ppm
in the Soderberg cells and 60-220 ppm in the prebake cells. It was
found to be difficult to correlate sodium levels to operational
parameters, because the sodium levels in individual cells varied in
a seemingly erratic manner that could not always be related to
recorded changes in operational parameters. This is demonstrated
in Fig. 9, where the variation with time is demonstrated. Over
short periods of time (Fig. 9a) the sodium remained relatively
stable, while for longer periods (b and c) the variations were large.
Fig. 9c shows that the cell under study after having stayed at a
high sodium level for a period of 20 days, dropped gradually to
quite low levels. The reason for this behaviour was not clear.
The following parameters were believed to have an influence on
the sodium content: temperature, acidity (excess AlF3), electrical
noise (current oscillations), and the alumina content.
The effects of bath temperature and excess AlF3 are depicted in
Figures 10 and 11. These two parameters are interrelated, since
there was a clear correlation between low excess AlF3 and high
Figure 9: Sodium content in individual prebake cells versus time. In (a) also data obtained with conventional sampling are shown.
J.Thonstad et al.
temperature, as expected when cells operate at constant so-called
superheat (temperature above the liquidus temperature). The
approximate trends in equilibrium sodium contents (i.e.
equilibrium with the bulk of the bath) are also indicated on the
figures, and one sees that: (1) the real sodium levels are far above
the equilibrium data, and, (2) the trends are opposite. This will be
discussed in the following.
It was found that the sodium content went down with increasing
noise. This can easily be explained by assuming that a high noise
level reflects fluid dynamic instability in the cell, e.g. a disturbed
metal pad, uneven current distribution, anode spikes etc. The
following regression equation was derived,
c(Na) / ppm = - 3.87 * t /°C + 6.5 * I /kA -
- 827 * El.noise /µΩ + 2872 (12)
As shown in Fig. 2, the alumina content in the bath has a minor
effect on the equilibrium sodium content. Nevertheless, tests in
pointfed, prebake cells of different technology showed
consistently that the sodium content varied during the normal
overfeeding-underfeeding cycle (e.g. 130 % and 70 % of the
actual consumption rate). As shown in Fig. 12, the sodium content
decreased during overfeeding and increased during underfeeding;
or in other words: the sodium content decreased with increasing
alumina content.
5 of 7
Discussion of industrial data
240 6.0
230 Na Al2O3 5.5
Although the average sodium contents for entire cell-lines can
220

c (Na) / ppm
remain very stable over long periods of time, individual cells 5.0

c (Al2O3) / wt %
show, as mentioned above, large and seemingly erratic 210
4.5
variations in the sodium levels. It is clear that we do not have 200
4.0
sufficient information about the forces that govern the sodium 190
3.5
level to be able to explain some of the variations. It is 180
particularly puzzling that the trends with respect to temperature 170 3.0
and AlF3 (Figs. 10 and 11) are opposite to what one would 160 2.5
expect from thermodynamics. Many possible explanations might 150 2.0
be proposed. However, as long as they have not been tested and 0 1 2 3 4 5 6 7 8 9
verified, such speculation may be of little value. Only a few time / hours
tentative ideas will be presented here.
Figure 12: Variation in the sodium content in the aluminium and
the alumina content in the bath in prebake cells during
350 overfeeding (0 – 4 hours) and underfeeding (4 – 8 hours).
300
Overheating can be used as one example. In case the cell gets
c (Na) / ppm

250 overheated, the sideledge will start melting. If the sodium in the
200 metal reacts with this melt, the metal may loose or gain sodium,
depending on the initial level and on the temperature. The
150 composition of the side ledge is close to that of cryolite [16], so
100 the metal will be exposed to two bath phases with different
compositions. Reaction with the near neutral molten sideledge
50
may then drive the sodium content down, in spite of the fact that
0 equilibrium with the bath phase at high temperature should have
945 950 955 960 965 970 975 980 985
the opposite effect.
cell temperature / oC
Reaction with sludge may have a similar effect as reaction with
Figure 10: The variation in sodium content in prebake cells molten sideledge. It is known that the bath phase in the sludge
versus bath temperature. Full line: linear regression line. Dotted tends to contain less excess AlF3 than the bath [24]. Keller et
line: trend in sodium contents that would be in equilibrium with al. [2] attributed this fact to a reaction between the sodium in the
the bulk of the bath. The regression is valid for cell current aluminium and the bath phase in the sludge. If equilibrium is
186.1 kA and electrical noise 0.13 µohm. established according to Eq. (7), where “melt” represents the
bath phase in the sludge, it is clear that the sludge will acquire a
considerably higher NaF/AlF3 ratio than the bulk of the bath.
350
Freshly formed sludge containing bulk bath may then extract
300 sodium from the aluminium and thus lower its sodium content.
c (Na) / ppm

250
If a cell cools off, some cryolite freezes out, and the content of
200 excess AlF3 in the bath increases. In addition to growth of the
150 sideledge, the cooling may lead to the formation of a slurry
containing solid cryolite at the bath-metal interface. Such a
100
slurry will inhibit mass transfer and thus raise the sodium
50 content in the metal.
0
7.5 10.0 12.5 15.0 17.5 In newly started cells the carbon lining absorbs appreciable
excess AlF3 / wt % quantities of sodium, which is taken from the aluminium. During
the initial period of cell life, lasting about two months, the cells
Figure 11: The variation in sodium content in prebake cells may tend to have low sodium contents while the lining acts as a
versus excess AlF3. Full line: linear regression line. Dotted line: sodium sink [25].
trend in sodium contents that would be in equilibrium with the
bulk of the bath. Appendix

We can suppose that a given cell has a stable operational mode
where it runs quietly (low noise), the temperature and the bath
composition are stable, the current efficiency is high and the
sodium level is high. If such a cell makes an “excursion” into an
unstable regime, this steady state is upset, the metal / bath
interface may be disturbed as well, and the sodium level may
drop.
Thermodynamic model
The model is based on the following assumptions and
approximations:
1. In the first step the composition co-ordinates of the system
NaF — AlF3 are transformed to the system NaF — NaAlF4.
This transformation does not reflect the real ionic

J.Thonstad et al. 6 of 7
 composition of the melt, but it is suitable to describe the
thermodynamic properties. When alumina or CaF2 are
present in the melt, we assume that these additions have only
a diluting effect.
2. The content of sodium in aluminium, which is in
equilibrium with the melt, can be described by the reaction,
Al(l) + 4 NaF(melt) = 3 Na(in Al) + NaAlF4(melt) (13)
The equilibrium constant of this reaction was calculated
from the thermodynamic data published in the JANAF
tables [17]. The standard Gibbs energy of formation of
NaAlF4(l) was taken from Sterten et al. [18]. At 1000 °C the
value of the equilibrium constant of reaction (13) was found
to be K = 3.25×10-4. The activity coefficients of sodium (and
of the other impurities) in aluminium were reviewed by
Sigworth and Engh [19]. The Henrian activity coefficient of
sodium in aluminium at 1000 °C in terms of mole fractions
equals 175.
3. The excess Gibbs energy of the system NaF — NaAlF4 is
expressed by the following equation (x(i) represents mole
fractions of the model components),
∆GE / (J mol-1) = x(NaF)x(NaAlF4) {a0 + a1x(NaAlF4) +
+ a2 [x(NaAlF4)]2 +a3 [x(NaAlF4)]3} (14)
where : a0 = - (956 ± 34)×102 + (43.97 ± 0.72) T / K;
a1 = - (249 ± 25)×103 + (202.3 ± 3.2) T / K;
a2 = (659 ± 56)×103 – (502.1 ± 6.7) T / K;
a3 = - (457 ± 40)×103+ (347.9 ± 5.0) T / K.
4. The parameters of this equation were determined by a non-
linear regression analysis (the criterion of least squares,
confidence level 99 %) using available experimental data for
the content of sodium in aluminium [1, 5-12], the vapour
pressure of NaAlF4 [20] and the solid - liquid equilibrium of
NaF with the melt [21]. For the enthalpy of mixing of the
system NaF – NaAlF4 the data by Holm [22] and by Hong
and Kleppa [23] were used.
11. V. Danielik, P. Fellner and J. Thonstad, J. Appl.
Electrochem. 28 (1998) 1265-1268.
12. V. Danielik and P. Fellner, Chem. Papers 52 (1998) 195-
198.
13. J. Zorić, I Roušar and J. Thonstad, Light Metals 1997, 449-
456.
14. J. Thonstad and S. Rolseth, Electrochim. Acta 23 (1978)
223–243.
15. P.V. Polyakov, V.M. Mozhaev, V.V. Burnakin, S.S.
Romanchenko, Electrochimiya 17 (1981) 1454-1459.
16. J. Thonstad and S. Rolseth, Light Metals 1983, 415-423.
17. D.R. Stull and H. Prophet, ‘JANAF Thermochemical
Tables 2nd’, ed. Nat. Bur. Stand. (USA), coden NSRDA
1971.
18. Å. Sterten and I. Mæland, Acta Chem. Scand. A39 (1985)
241-257.
19. G.K. Sigworth and T.A. Engh, Scand. J. Met. 11 (1982)
143-149.
20. J. Guzman, K. Grjotheim and T. Østvold, Light Metals
1986, 425-429.
21. A. Solheim and Å. Sterten, Proc. of Ninth Int. Symp. on
Light Metals Production Tromsø – Trondheim Norway
August 19 – 21 1997, 225-234.
22. J.L. Holm, ‘Thermodynamic properties of molten cryolite
and other fluoride mixtures’, Institute of Inorganic
Chemistry, NTH, Trondheim, Norway, 1971.
23. K.C. Hong and O.J. Kleppa, High Temp. Science 8 (1976)
299-307.
24. J. Thonstad, F. Nordmo and J.B. Paulsen, Met. Trans. 3
(1972) 403-408.
25. H.A. Øye, J. Thonstad, K. Dahlqvist, S. Handå, V. De
Nora, Aluminium 72 (1996) 918-924.

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