Eierrrwkimio ACT. Vol. 25, pp. 131-137.

Rrgamon Press Ltd. 1980. Printed in Great Britain.

CURRENT EFFICIENCY AND BACK REACTION
IN ALUMINIUM ELECTROLYSIS
B. LILLHIUEN and S. A. YTTERDAIIL
Norsk Hydra as, Research Centre, 3900 Porsgrunn, Norway
and
R. HUGLEN and K. A. PAU~RFN
Norsk Hydra a.s, Karm#y Fabrikker, 4265 Havik, Norway
Abstract - The rate of back reaction in aluminium electrolysis is discussed in terms of mass transfer theory.
The rate of dissolution of aluminium seems to be the most important step in this reaction.
By using the physical.data which are available in the literature, current efficiency variations have been
calculated as a function of the most important parameters in the electrolytic cells. These calculated variations
agree reasonably well with experimentally determined variations.
1. INTRODUCTION
Current efficiency is one of the most important para-
meters that are being used to characterize the working
condition of an aluminium electrolysis cell. The cur-
rent efficiency provides information which is relevant
both to the energy consumption and to the metal
output of the cell. Accordingly, a large number of
experimental investigations has been made[l-31 in
order to define cell working conditions that secure a
high current efficiency.
The present work is an effort to approach the
current efficiency problem both from a theoretical and
from an experimental point of view. Similar theoretical
efforts have recently been made by Rob1 et al[14].
2. THEORETICAL PART
2.1 Back reaction rates
It seems to be widely accepted[4,6] that the current
efficiency loss in aluminium electrolysis cells is mainly
due to the back reaction between metal and anodegas:
Al + ;C02- fAl,O, + +ZO.
(1)
Other explanations have been suggested[5], which
may have some significance, but we will in the
following assume reaction (1 j to be solely responsible
for current elI?ciency losses. We will in addition make
the following assumptions :
(a) Reaction (1) occurs between dissolved reactants.
(b) The simple film theory is vahd, and we disregard
the transportation of the heat of reaction and
the reaction products.
(c) The chemical reaction between dissolved metal
and dissolved carbon dioxide is instantaneous:
and the rate of reaction (1) is considered to be
controlled by the mass transfer rates ofdissolved
reactants through stagnant films.
Experiments have indicated the chemical reaction to
be much faster than the mass transfer processes
involved[4].
Up to this time, most authors have concluded that
the back reaction occurs between dissolved aluminium
and gaseous carbon dioxide[b]. We believe, however,
that the following calculations lend support to a
reaction model that involves dissolved carbon dioxide
as well as dissolved aluminium.
If the assumptions we have made above are valid, we
may, according to Aarebrot et al[7,8] write for the
dissolution rates of aluminium and carbon dioxide:
k c ,, . Go,
h, . (3, >
ICXl - CA,) (2)
where
r = dissolution rate
A = interfacial area against electrolyte
k = mass transfer coefficient
C = concentration of dissolved species in the bulk
electrolyte
C* = thermodynamic solubility.
Note the implication From assumption (c) that from
C,, > 0 follows that Go, = 0 and uice uerso C,, z 0 ,
makes C,, = 0.
Combining (2) and (3), and introducing the sto-
chiometric requirements of (1) lead to the following
expression :
x Cl + k)!!$jCct,- Gil
[I + ($J(@m, - C,,l = ;. (4)
The interfacia1 area between metal and electrolyte is
obviously smaller than the area gas/electrolyte. The
ratio A,JA,,, will depend upon bubble size, metal
dispersion, side crust profile and metal pad height etc.
As a first guess, based on observations in plant cells
and ofgas-bubble behaviour in a hydraulic model cell,
we estimate this ratio to 0.1. By using (23) in the work
of Aarebrot (8) we estimate the ratio k,,/k,-ol to 1.0.
131
132 B. LILLEBUEN, S. A. YTTERDAHL, R. HUGLEN AND K. A. PAULSEN
Both of these estimates contain of course consider-
able uncertainty, and further refinement should be
encouraged. In this respect a precise determination of
the diffusivity coefficient of dissolved CO2 would he
very useful. We have adopted a value for Dco, =
iOmE .m2 -s-[9] and for D*t = 3 .10-s .
mz *s-[lo].
We proceed by assuming a finite amount of dissol-
ved aluminium to be present in the bulk electrolyte,
and write
C*, = f. CXI (5)
where f is the fraction present (relative to thermody-
namic solubility).
By inserting (5) into (4), remembering that CA, > 0
implies Ccoz = 0, and setting[6]
Cx, = lOed mol .IXII-~ (uncertain)
Go,, =
2. 10m6 mol .crnm3
we find:
f= 0.113
which means that the bulk electrolyte contains approx
1.13 . lo- mol cm- of dissolved aluminium at steady
state. The frequently discussed question of which step
in the back reaction that is rate determining, cannot of
course be definitely answered by means of such
calculations. We would like to suggest, however, on the
basis of these calculations, one probable concentration
pattern for the interelectrode gap of an aluminium cell,
as shown in Fig+ 1. The model developed by Rob1 er
al[14] is based on a similar concentration pattern.
The dissolution rate of carbon dioxide equals that of
aluminium in spite of the smaller solubility for carbon
dioxide. This is possible because the dissolution rate of
the gas will be increased due to the finite amount of
dissolved aluminium in the bulk electrolyte, and
because of the large interfacial area for the gas.
Since a very small increase in the bulk concentration
of dissolved aluminium is sufficient to bring about a
substantial increase in the carbon dioxide dissolution
rate (3), we will assume, from the calculations above,
that the physical dissolution of metal from the cathode
l Di ssol ved AL
ANODE
o Dissolved CO,
c-o
c/concentration
CATHODE
Fig. 1. Concentration profiles (schematic) for dissolved
ahuninium and dissolved carbon dioxide in the electrolyte of
an aluminium electrolytic cell.
is (still disregarding the possibility of metal disper-
sions) the rate determining step in the back reaction.
The rate of the back reaction is then:
r = rA, =
&I . k*, . aI11 9)
z 0.887/l,, . k,, cx,.
(61
Following Aarebrot[7,8], the mass transfer coef-
ficients can be calculated from
Ns,, = O.O~~N;,=IV:;~~
(71
where
Sh _ ht.21
---
D*,
(10)
For the physical properties we assume the following
values[6, lo]
density of electrolyte p = 2050 kg/m3
viscosity of electrolyte p = 3.10-3Pa*s
diffusivity of dissolved metal DM = 3 . lbzB m/s
interelectrode gap
i tm)
interfacial velocity
V, (m/s)
(velocity of metal relative to
electrolyte)
The finat expression for the mass transfer coefficient
becomes
k,, = 1.540. 10-a. Yf .63 .I -0.17
111)
and for the back reaction
r = 1.366 . 10m4 . AAl - VO,, . l-o.17 . CX,.
(12)
Current efficiency is defined by
(13)
where r. is the amount of metal produced with 100%
current efficiency. Inserting r from (12) into (13) yields
finally
lo-. A,~- V:.E3 .l-o.17 .CX,
1
lW.
J -0
(14)
Equation (14) is useful for predicting how the current
efficiency will vary with parameters like metai area,
in&-electrode distance, metal solubility, and inter-
facial velocity.
2.2 Variation of current efficiency with interelectrode
distance
Assuming q = 90/, for I = 0.06 m gives by (14) the
correlation shown in Fig. 2.
Figures 3-5 gives the expected variations, as calcu-
lated from (14). We have somewhat arbitrarily as-
sumed q = 90% for V, = 0.10 m s- , AL = 1.5 mjm
anode area and Cx, = 0.05 wt%, respectively, since
Current efficiency and back reaction in rtluminium electrolysis
90
1 2 3 4 5 6 7 8
I/cm
Fig. 2. Current efficiency, q. calculated as a function of interelectrode distance (I).
i -
I
I I I I I
F
90 -
60
I I I I I I _
0.02 0.04 0.06 0.0 8 0.10 0.12
c&&J t %
Fig. 3. Current efficiency, 1. calculated as a function of Al-solubility, (CX,), in the electrolyte.
Eh 25/21
801
I t I
1.0 1.5 2.0
A,, /cmz/c~
Fig. 4. Current &ciency, 0, calculated as a function of metal area per unit anode area (A,,).
-_
133
134 B. LILLEBIJ EN, S. A. YITERDAHL, R. HUGLEN AND K. A. PAULWN
Fig. 5. Current efficiency, Q, calculated as a function of the metal interfacial velocity relative to the electrolyte
(VJJ
precise data are lacking. From the correlation between
current efficiency and metal solubility (Fig. 3), together
with experimental data for metal solubility as a
function of temperature[ll] and oxide content in the
electrolyte[6], we have calculated the variation of the
current efficiency with temperature, and with the oxide
content in the electrolyte. Metal solubility data in the
literature are conflicting, but the calculated cor-
relations are compared with experimental ones in the
discussion of the experimental data given later.
3. EXPERIMENTAL
Current efficiency was determined on Siiderberg
type cells by measuring the CO/COI ratio in the anode
gas,
and assuming the well-known Pearson-
Waddington formula to be valid :
q = 100-5o
c
%CO
%CO+%CO,
>
(15)
The anode gas analysis was made by gas chromatog-
raphy. The sum of %CO and %C02 was aIways close
to 100A, except during anode effects.
The gas was sampled by means of 121 in. dia iron
tubes that followed the anode mass down into the melt.
The gas was filtered before sampling, and for the
Boudouard-reaction to have small significance we
found it necessary to maintain a steady gas-flow of at
least 200 N ml/min. The tube was periodically blown
with pressurized air to remove dust in the system.
In general the anode gas analysis gave current
efficiencies that were 2-3% lower than the actual
values, as judged from the metal production. This is
probably due to the effect of the Boudouard-reaction
on the gas composition[GJ However, as long as the
gas-flow remains steady, we believe this to be a rather
constant error with littie influence on the correlations
under study. Attempts to calculate corrections to the
gas analysis for the temperature dependence of the
Boudouard-reaction rates were not very successful due
to conflicting rate data. The effect of such corrections
on the correlation between current efficiency and
temperature was in any case modest, and we have not
included these corrections here.
4. RESULFS AND DISCLJ SSION
Results from current efficiency measurements are
plotted in Fig. 6 and 7. Operations on the cell, like crust
breaking, tapping of metal etc have been indicated on
the figures, The occurrence ofanode effects is seen to be
the dominant factor for the dynamics of the cell.
The variations in the oxide content of theelectrolyte
as well as in the electrolyte temperature are shown in
the same figures. Electrolyte samples for analysis were
taken under the anode, and care was exercised to avoid
physical oxide in the samples.
Results from regression analysis of the experimental
data from two direrent runs are shown in the table
below (cf Figs 8-9).
Some important parameters like bath acidity and
the interelectrode distance were not measured during
these experiments. This may partly explain the differ-
ence in the result from run no. 1 as compared to those
from run no. 2. Also, as seen from Figs 6 and 7 the
observations in run no. 2 have been made during a
period with frequent anode effects, and this may have
disturbed the gas compositions, since some primary
CO may be formed during anode effects[6]. Further-
more, the data from run no. 2 are much more scattered,
and the regression model are only able to explain
about 31.6% of the variations, while it explained 58.5%
in the data from run no. 1. Theconfidence intervals for
the regression coefficients are likewise much larger for
the data from run no. 2.
Equation (14) can obviously be used to calculate
how q should vary with for instance temperature, if we
know the relation between Al-solubility (CX,) and
temperature, and assume all the other parameters of
(14) to remain constant. The same calculations may be
carried out for q =f(C,,,,,). This is shown, in com-
parison with experimental data, in Tables 2 and 3.
Solubility data have been selected from[6,11,12].
It should be noted that BC:,/BT in Table 2 has been
measured in melts saturated with A1,03, and the
Current efticiency and back r eac t i on in aluminium electrolysis 135
Fig. 6. Current efficiency, 1. oxide content, C*,,ol. and temperature, T, variations with time during run no. I.
AE indicates anode ef f ec t s, CB crust breaking and TP tapping of metal.
12 16 20 24 04 08 12 16 Ti me
Fig 7. Current efficiency, n. ox i de c ont ent , CA,,03, and temperature, T, variations with time during run no. 2.
AE i ndi c at es anode effects, CB crust breaking and TP tapping of met at .
Table 1. Regression analysis on current efficiency data from two different runs
Regression model
Calculated coefficients
and 90% confidence intervals
Run no. I Run no. 2
q=A+B*(T-T) A: 84.7*0.3 A : 83.6 + 0.3
B: -0.183+O.B6 B: --0.279+0.1
S: 30.6% S: 28.5%
tl = A + C . (CAIN, - CM,,,) A : 84.7 +0.3 A: 83.6 +0.4
C: 0.565kO.2 c: 0.05-t_o.33
S: 27.7% s: 0.1%
q = A+i 3-(T-T)+C~(C,,,o,-
~*,,J
A : 84.7 + 0.25 A : 83.6 i 0.3
B: -o.1i33+o.o5 8: -0.304~0.1
c: 0.467+0.16 C : 0.275 + 0.29
S: 58.5% S: 31.6%
T ad CA,~O>
are the arithmetic mean values, being 9753C and 3.133 wt/_ in run no. I ; and
977.2C and 3.197 wt? in run no. 2. S is % variation in q which is explained by the regression
model. Interaction terms bctwecn T and CAIzoa were not found significant.
136 B. LILLEBUEN. S. A. YTFERDAHL, R. HUGLEN AND K. A. PAULSEN
90
M RUN1
A--.,3 RUN2
a
0
. 560 970 980 990
T/W
Fig. 8. Current efficiency, q, plotted US melt temperature. 9 is averaged over 1C ranges.
80
75
s
A
n
M RUN 1
A---A RUN 2
I 1
1 2 3 4
Fig. 9. Current efficiency, q, plotted 0.7 oxide content, C *Izoj. q is averaged over 0.5 wt% AI,O, ranges.
Table 2. Measured and cakulated current efficiency correlations with electrolyte
temperature
Data used
in (14) Calculations by (14)
Measured
correlations
3.10-4[11]
5.5.10-4[12]
_
-0.06
-0.11
-(0.087-o.138)~13]
-0.139[1]
- (0.183-0.304)
(present results)
Table 3. Measured and calculated current efficiency correlations with oxide content in
the electrolyte
_~
Data used Measured
in (14) Calculations by (14) correlations
--!Y.sL (wt%/wt%)
acAl,o,
-4.10- [6] 0.8 1.0[13]
0.05-0.567
(present results)
Current efficiency and back reaction in aluminium electrolysis 137
increase of C:, with increasing temperature is pro-
bably larger in melts with lower Al&,-content[6].
With this in mind, the calculated correlations seem to
be of the same orders of magnitude as the measured
ones, which should encourage a further pursuit of this
approach to current efficiency. Such studies should
include precise measurements of metal- and gas-
solubilities, and the corresponding diffusivities. In
addition the possibility of getting metai disper-
sionsC7, S] should be further investigated, and also the
size and behaviour of the carbon dioxide bubbles. The
relative velocity metal-electrolyte at the interface is
also highly important.
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