300C ,IOURNAL OF THE ELECTROCHEMICAL
a practical unit became available, was adopted generally by
the aluminum industry. Today, about 1,750,000 kw of recti-
tiers are in operation in this service. The tremendous demand
for aluminum, which developed during the World War II
period, and the national power shortage, led Alcoa tn initiate
the use of natural gas engines for direct drive of (1-c genera-
tors. The next step away from hydroelectric power is the
building of a plant in Texas employing lignite as a fuel to
make high-pressure steam to supply power for generating
current for the reduction of aluminum, In 1951, approxi-
mately 4 per cent of the nation's electric power was consumed
in the electrolytic production of aluminum.
Fie,. 3. Top view of modern cell for electrolytic production
of aluminum; rectangular baked carbon anodes and their sup-
ports are shown, together with bins from which alumina is fed
to the bath.
The development of cells for the electrolytic reduction of
aluminum can also be traced through the types of anode
employed. Carbon anodes of high purity are required, because
metallic impurities in the carbon are reduced and contami-
nate the aluminum. The conductivity, mechanical strength,
R e c e n t D e v e l o p m e n t s in Alumina Electrolysis as Found in French
and Italian Publications
F. V. A n d r e a e ~
During the years 1948-1950, under the chairmanship of
Louis Ferrand, the third section of the Soci~t6 fran~aise des
Electriciens (electrochemistry, electrometallurgy, and electro-
thermics) devoted a number of meetings to the study of elec-
trolytic solutions in molten cryolite in order to shed some
light on the theoretical aspects of this electrolysis which is
of such industrial importance. Appended to this summary is
a list of the papers under consideration, (1-4), including the
remarkable studies made by A. Vajna in the research labora-
tories of Mori during the last few years.
The following commentary deals particularly with the
Electrical Engineer, 351 Derby Circle, Chattanooga, Ten-
nessee.
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SOCIETY November 1952
resistance to oxidation, and other characteristics are impor-
tant in the efficient operation of the process, and have all
been given attention in developing satisfactory anodes. The
('ell shown in Fig. 1 employed prebaked cylindrical anodes
about 4 in. in diameter. With increase in cell capacity, the
size of anode increased and the shape was eventually changed
to anodes with square or rectangular cross section. The 1902
anodes were supported by iron or copper rods either wedged
or threaded in the upper end of the carbon anode. The large
modern rectangular anodes have a steel stub fastened in the
head of the anode by cast iron ; they are supported by a copper
bar which is bolted to the stub and clamped to the anode bus.
Some 25 years ago, the Soderberg continuous, self-baking
anode was tried out by the aluminum industry and found
to have certain advantages. Through years of use the Soder-
berg anode has been improved, particularly with respect to
the current leads and the method of support. At the present
time both prebaked and Soderberg anodes are used in pro-
ducing aluminum. Since approximately two-thirds of a pound
of carbon is consumed per pound of aluminum produced, the
electrode-carbon requirements of the industry are tre-
mendous.
In 1902, the production from a single cell was about 175
lb per day with a power consumption of over 12 d-c kwhr/lb.
The modern units produce about 750 lb per day with a con-
sumption of about 8.5 d-c kwhr/lb. Of course, electric power
is required for other plant operations and values of 9 or 10
kwhr/lb are sometimes employed for calculating the over-all
power requirements of the aluminum works.
In a little over fifty years, aluminum has risen in useful-
ness and volume to challenge for leadership among nonferrous
metals. In the last eleven years two new concerns, the Rey-
nolds Metals Company and Kaiser Aluminum and Chemical
Corporation, have become competitors of Alcoa as producers
of aluminum in the United States. This is now the out-
standing electrochemical industry in point of power con-
sumption, and the United States and Canada are producing
the major part of the world's aluminmn requirements. The
production in 1951 was approximately 1,283,000 tons, and
by 1954 an annual production of over 2,000,000 tons is antici-
pated. The available reserves of ore give promise that alu-
minum can still look forward to a long period of growth.
most recent articles which appeared in the January and
February 1952 numbers of the Bulletin of the Soci~t~ fran-
~aise des Electriciens. 2
W o r k of Dr. D a r m o i s a n d S t u d e n t s
In works of varying importance E. Darmois of the Paris
Faculty of Sciences, followed by some of his most recent
students, Messrs. Doucet, Chalin, Rolin, Petit, Mergault,
Zarzicki, and Miss Sutra has demonstrated the general appli-
cability of Raoult's law, both to solutions of molten salts, at
This publication is available through the Society, 14 Ave-
nue Pierre-Larrousse, Malakoff, Seine, France. 400 French
francs.
 Vol. 99, No. 11 FIFTY Y E A R S OF I N D U S T R I A L ELECTROLYSIS 301C

high and low temperature, and to aqueous solutions (5)

provided that the saline medium possesses the fundamental
i+ ANODE + ]
property of a pure solvent: that of melting at a constant 02t" 4e 1/202+ 2e 02+4e 1/20,'Z+2e
temperature.
These experiments proved that Raoult's law is a limiting
law which applies rigorously to the ideal solutions, which, in
practice, are the very dilute solutions. This law is, therefore, 3F- Ar
T
Am~ O= A?*~-~!,02-
accessible to direct observation only when the results of ex-
perimentation are recorded with great exactness and absolute
precision, permitting accurate extrapolation. A IF3"o-- At F6N03
T/
AI203 AI203
Under these conditions (Raoult himself showed how to
apply his formula) the molecular temperature drop for in-
finitely dilute solutions can be written (At)/m = nK; At repre-
1
3Na +
L AI +++ AIO§ 0=
sents the measured drop in temperature in degree C of the
melting point caused by the introduction of m moles of the
solute in 1000 grams of solvent, K the cryoscopic constant, AI 3e AI 3e
ill
AI 3e At 3e
and n the number of dissociated ions.
This cryometric method is, therefore, simply a means of I- GATHODE -I
counting the dissociated ions and consequently of deter-
mining the composition of complex ions which do not disso- In this last case one can assume that the electrolytic mech-
ciate any further. The ions common to those of the solvent anism progresses as follows:
are the only ones that are not counted. This method is in 1. At the anode, an O= ion is discharged "rod the complex
complete accord with recent conceptions, more particularly ion AlOe- is discharged to form O2 and an A1+++ ion.
with Debye's theory, in accordance with which the salt 2. At the cathode, the A10 + ion forms A1+++ ion and O=
solutions must be considered as totally, or almost totally, ion, the former being discharged at the cathode while the
ionized. latter must migrate to the anode.
One of Professor Darmois' students, Maurice Rolin (6-8), Thus is explained the apparent anomaly of finding a cation
has very dearly developed the mechanism for the dissociation A1+++ at the anode and O - - at the cathode and the com-
of alumina dissolved in a bath of molten cryolite. The validity plicated circuit which these ions have to travel to arrive at
and applicability of Rolin's observations were discussed at the end of the electrolytic process.
the December 21, 1950 meeting of the French Society of Actually there exists a general state of dissociation in ac-
Electricians. There follows a summary of some of the per- cordance with the left and right thirds of the diagram (per-
tinent conclusions arrived at by Rolin. haps even with all three sections, at low concentrations), and
The melting point of molten cryolite was found to be it is simply the value of the applied potentials or the ionic
1006~ or 1279~ Since the molecular heat of fusions is concentration which determines which ions are discharged.
16.64 cal/g mole, Van't Hoff's formula permits the calcula-
tion of its cryoseopic constant (40.8), which is verified by Contributions of A. V a j n a
the cryoscopy of chlorides and fluorides.
Special consideration must here be given to the work of
The molecular state of molten cryolite is given by the
A. u (9-16), not only for the wealth and novelty of the
equation:
physicochemical data presented to the electrochemists, but
also for the originality of the experimental method employed,
AIF6Na3 --+ AIFs + 3F- + 3Na +
which included direct observation of the phenomenon under
study. Special attention is called to the photographic repro-
and that of dissolved alumina in the electrolytic baths by ductions made with the help of a microelectrolyzer (13, 15,
the two equations: 16).
Such a brief article must limit itself to a few remarks
AhO~ --~ A102 + A1+++ + 0 - - ( 3 ions) (I) concerning two reports made by the author to the Soci6t6
fran~aise des Etectriciens, at its meetings of May 31 and
AI20~ --* AIO~ + AIO+ (2 ions) (II) June 4, 1951 05, 16).
In the first paper the data on the critical current density
the first equation applying to very dilute solutions (below confirm, with certain slight modifications, the results ob-
0.2~), the second to industrial concentrations. tained by the Russian scientists Schiskin, Karpatchef, and
Under normal operation, during electrolysis, only the alu- I)olgof. The existence of this critical current density can be
mina ions are discharged, while the cryolite, although ionized, used to calculate directly the concentration of alumina dis-
does not participate in the electrolysis, and the appearance solved in industrial baths. Mr. Ferrand has made an inter-
of Na+-ions constitutes only a secondary and parasitic phe- esting application of this method in a new apparatus which
nomenon. predicts the anodic effect (17) and is especially useful with
The lnechanism of electrolysis is illustrated it, the diagram the contimmus feeding of alumina which he proposes and of
below, in which three compartments are shown. On the left which more will be said below (18).
is shown the ionization of nonelectrolyzed cryolite, in the In his study of the capillary effects at the anode under
center the discharge of the alumina ions at very low concen- normal tmd upset operation, Dr. Vajna concludes that the
tration, and at the right the dissociation of alumina at in- amorphous carbon is wetted in a molten cryolite bath of any
dustrial concentration, by means of complex ions such as composition only in the presence of oxygen. Since the wetting
A10,.- at the anode and AIO + at the cathode. of the anodic surface is necessary to the passage of the cur-

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 302C JOURNAL OF THE ELECTROCHEMICAL
rent, it follows that the oxygen must appear first at the anode,
and that, under normal operation, CO and CO~ are second
ary products. Otherwise the bath would not wet the anode.
These observations confirm Rolin's conclusions regarding
the primary dissociation of dissolved alumina.
The second paper does not reach such precise conclusions
as the preceding one, and according to the author must be
considered as the prelude to other studies regarding the
kinetics of the secondary reactions which affect the current
efficiency.
Some very unusual photographs taken on a microelectro-
lyzer clearly show the existence of a metallic fog between the
two poles. Using the lead rinsing method suggested by
Pearson and Waddington (19) it is found that the metallic
fog is mostly sodium and is denser in neutral and alkaline
baths than in acid baths. This explains why the current
efficiency is higher in acid baths than in neutral or basic
baths, other conditions being equal. This opinion regarding
the nature of the metallic fog and the role it plays in the
midst of the anodic gaseous phase is confirmed by Frejacques
(4).
The second part of the paper is devoted to a tentative cal-
culation of the diameter of the gas bubbles under the anode,
under simplified assumptions. The author figures that the
diameter is about 0.7 cm and is independent of the type of
the bath and of the time of contact and the geometric shape
of the anode.
F i n d i n g s of L. F e r r a n d
Louis Ferrand, whose innovations in the field are widely
recognized, spoke at the April 26, 1951 meeting of the
SociSt~ fran~aise des Electriciens on the continuous dissolving
of alumina (18), which in accordance with one of his pat-
ented processes (20) would practically elinfinate the anode
effect and replace manual or semimechanical methods of
distributing alumina by entirely automatic methods.
At the June 19, 1952 meeting of the SocietY, Ferrand (21)
presented his ideas regarding the properties of dilute elec-
trolytes, with interesting remarks concerning the dissociation
of alumina in baths of industrial concentrations, based on
the latest publications (22).
All authors agree in recognizing the bad effects of the anode
effect (23). To eliminate it completely, or at least to space it
to the same rhythm as the tapping, would represent con-
siderable progress and would result in a greater stability of
operation, especially in the control of the temperature and a
saving of the fluorine-bearing materials.
The discontinuous feeding of alumina makes use of the
central free space in the case of prebaked electrodes (24), or
of the peripheral space in the case of Soderberg self-baking
electrodes.
The semicontinuous feeding, which is an alternative to the
preceding method, does not require such large volumes of
bath in order to get the same spacing of the successive anode
effects, since it employs preventive feeding at regular inter-
vals without waiting for the anode effect, and submits to the
anode effects only at distant intervals. This method is in
general use in the United States, Canada, and Russia.
At Kaiser's Tacoma Plant the cells are fed regularly every
six hours. The anode effect is allowed to take place only when
the cell becomes muddy. By this method an average of 0.6/
0.7 disturbance per day is reached, or a disturbance every
36 hours. The same procedure is used at the Spokane plant
where the disturbances are about 24 hours apart, considered
too frequent. At the Reynolds Listerhill Plant the disturb-
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SOCIETY November 1952
ances also occur about every 24 hours with feedings every
six hours, one time on one side, the next on the other side.
Based on the conclusions reached by Dr. Vajna in study-
ing the viscosity and conductivity of the bath (10, 11),
Ferrand shows very clearly the disadvantage of this method
of feeding, which is liable to result in alumina deposits on
the conductive bottom when alumina is fed through the
central opening. In an)" case this method results in a con-
stantly changing alumina concentration which goes from a
maximum of 7-8 per cent to a minimum of 1-2 per cent,
passing suddenly from the minimum to the maximum at the
time of feeding. This continuous variation of the concentra-
tion brings about a sudden drop in conductivity of the bath
and of its temperature, followed by a slow rise in tempera-
ture and an increase in conductivity between two feedings,
which naturally makes any control very difficult. It is to
eliminate such disturbances and make automatic regulation
of voltage and temperature easier that the author has de-
veloped the continuous oscillation of the anode, which per-
mits a continuous feeding of the alumina. His work is based
in part on the free fall speed of the alumina grains, as deter-
mined by Dr. Vajna (10). The linear motion of the anode at
the surface of the bath is of the order of 3 ram/rain (0.12 in./
rain) and the power to move the anodic equipment at this
slow speed is about 1/2000 of the total power input; it is
therefore negligible. On the other hand, manpower can be
entirely eliminated if the alumina is fed by compressed air
through a system of pipes which reach above the spaces be-
tween the anodes. During the test, the speed of the particles
in the bath was about 0.ll gram/cm2/min, compared with
2.~3 gram/cm~/min in the case of discontinuous feeding by
means of a poker. The motion of the particles, therefore, is
always much slower than the speed of free fall and there is
no chance for the particles to reach the bottom before they
are dissolved. Since the arrival of the alumina is also continu-
ous, there are no dust losses.
Besides its important savings in manpower and energy,
this method has the advantage of permitting, for a given
interpolar distance, operation at a higher current density
9rod, therefore, higher power input. This is because the con-
trol of the voltage at the terminal of the cell can be performed
in a bath of low alumina content, constant temperature, and
therefore of higher conductivity (about 12%).
With these baths approaching the conditions under which
the anodic effect takes place, it is necessary to have a sys-
tem which will predict the anodic effect. Such a system is
described on page 100 of reference (18). This system permits
the control of the speed or amplitude of the anodic oscilla-
tion, or both, so as to keep the alumina content constant. It
is only necessary to adjust the current density in the pilot
anode in such a manner that a signal be given when the
alumina concentration has dropped, for example, to 0.2 per
cent above the concentration at which the anodic effect will
take place. The idea is to maintain at all times conditions of
optinmm operation which unfortunately are close to those
at which the anodic effect takes place--a stop signal is there-
fore absolutely necessary.
W o r k of J. B o u c h a r d
During tile same April 26 meeting, J. Bouchard, after first
presenting his personal views concerning the development of
self-baking electrodes, discussed a few more special problems
concerning the generation and evacuation of anodic gases (25).
Based on the studies of Dr. Vajna regarding the surface
tension and the viscosity of the baths (9, 10), he tried to de-
 Vol. 99, N o . 11 F I F T Y Y E A R S OF I N D U S T R I A L
termine the speed and the time of sojourn of the gases under
the anode, and from there to suggest certain methods by
which the path of the gases under the anode can be shortened,
their evacuation facilitated, the time of contact lessened, and
the current density increased.
Bouchard presents two possible solutions leading to im-
provements in the design of self-baking electrodes for high
currents:
1. Cells with several anodes, which for 50,000 amperes
would number four, each measuring 200 x 75 em (80 in. x 30
in.) or a total of 60,000 cm 2 (9600 in.2). In such a design, the
average path under the anode compared with one anode of
70,000 cm :, which, moreover, cannot carry any larger cur-
rent, is reduced from 37 to 16 cm. This design also permits
the application of the Ferrand process of oscillating anodes
and the use of continuous feeding of alumina, besides the
automatic regulation with separate control of each anode.
To apply this oscillating movement without too much power
consumption would require passing the axis of oscillation
through the center of gravity of the anode. This reduction of
the anodic path, and the larger perimeter of the anodes should
increase the liberation of the gases and increase the propor-
tion of CO in the gases, retarding Boudouard's equilibrium
and, therefore, reducing the carbon consumption. This is
very important with self-baking electrodes, whose carbon
baked at low temperature is more reactive, and has a tendency
to increase the carbon consumption.
2. Cells with annular electrodes, as recently suggested by
Ferrand, where several annular anodes (two or three), ar-
ranged concentrically around a central axis and individually
controlled, permit both the increase of the interpolar dis-
tance from the periphery to the center, in the direction of
gas liberation, and the control of the distribution of the total
current among the various anodic rings. With such a design
the Boudouard equilibrium is still more retarded than in the
preceding case, not only because of the smaller mean path,
compared to a round electrode of the same cross section, but
mainly because of the higher speed at which the gases are
liberated, and the shorter time of contact caused by the con-
ical shape of the anodic surface and the forced withdrawal
of the gases through the central chimney.
REFERENCES
:Ill of the following articles except two are written and titled in
French, but the titles have been translated for the convenience of
the reader.
1. I. CADARIU, "Sur la tension 61ectrolytique de d~composi-
tiou de l'alumine." (The decomposition voltage of alu-
mina). Bull. soe. franr ]~lec., 6th series, 74, 531-539
(1947).
2. R. GADEAU,"Reflexions sur la thdorie de l'dleetrolyse dans
les cuves s aluminium." (Comments on the theory of
electrolysis in aluminum cells). Bull. soc. fran~. Elec.,
6th series, 74, 540-544 (1947).
3. J. BOCQUENTIN,"Contribution s la mesure de la tension
d'dlectrolyse dans les cuves s aluminium." (A contribu-
tion to the measurement of the electrolytic potential in
aluminum cells). Bull. soc. franc. Elec., 99,677-683 (1949).
4. M. FREJACQUES, "Etat actuel des thdories de l'dlectrolyse
de l'aluminium." (Present status of the theories on the
electrolysis of aluminum). Bull. soc. franf. ~lec., 99,
684-692 (1949).
5. E. DARMOIS,"Les lois de Raoult et leur aspect moderne."
(Raoult's laws and their modern applications). Bull.
Soc. chim. France, 5th series, 17, I (1950).
6. M. ROLIN, "Cryoscopie dans la cryolithe fondue et l'ion-
isation de l'alumine et des oxydes dissous." (Cryoscopy
in molten cryolite and the ionization of alumina and of
dissolved oxides). Thesis. Paris. (1950).
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ELECTROLYSIS 303C
7. M. ROLIN, "Cryoscopie dans la cryolithe fondue et l'ion-
isation de l'alumine et des oxydes dissous." Rev. m~t.,
48, No. 3 (1951).
8. ~I. ROLIN, "Cryoscopie dans la cryolithe fondue et con-
stitution ionique de l'alumine dissoute." (Cryoscopy in
molten cryolite and ionic composition of dissolved
alumina). Bull. soc. fran~. E,lec., 7th series, 13, 35-46,
D 47-55 (1952).
9. i . VAJNA, "Tension de ddcomposition de l'alumine et md-
canisme de l'dlectrolyse dans les fours industriels."
(Potential of alumina decomposition and mechanism of
electrolysis in industrial furnaces). Alluminio, 6, 599-
602 (1949).
10. A. VAJNA, "Viscositd des bains d'61ectrolyse de l'alumi-
nium '~ base de cryolithe h l'dtat de fusion." (Viscosity
of electrolytic aluminum baths of molten cryolite). A1-
ll~minio, 2,135-145 (1950).
11. A. VAJNA, "Sur la conductivit6 61ectrique des bains d'61ec-
trolyse de l'aluminium s base de cryolithe ~ l'6tat de
fusion." (On the electric conductivity in electrolytic
aluminum baths). Alluminio, 3, 215-224 (1950).
12. A. VAJNA, "Sur la densitd des bains d'dlectrolyse de l'alu-
minium ~ base de cryolithe s l'6tat de fusion." (On the
density of the electrolytic baths of aluminum dissolved
in molten cryolite). Alluminio, 8, 541-547 (1950).
13. A. VAJNA, "Tensions superficielles des baths cryolithiques
h l'dtat de fusion." (Surface potential of cryolite baths
in the molten state). Alluminio, 1, 29-38 (1951).
14. A. VAJNA, "Mesures de la resistivitd dlectrique des md-
langes alumine-cryolithe s l'dtat solide." (Measurements
of the electrical resistivity of mixtures of alumina-cryo-
lite in solid state). Alluminio, 2, 147-149 (1951).
15. A. VAJNA, "Tension d'dlectrolyse de l'alumine en rdgime
normal et en r6gime trouble dans les bains d'dlectrolyse
base de cryolithe ~ l'dtat fondu." (Voltage for the elec-
trolysis of alumina in normal and disturbed states in
electrolytic baths of molten cryolite). Bull. soc. franf.
~lec., 7th series, 14, 85-91 (1952).
16. A. VAJNA, "Facteurs physiques de rendement de courant
dans les bains d'dlectrolyse s base de cryolithe s l'dtat
fondu." (Physical factors in the current efficiency in
electrolytic baths of molten cryolite). Bull. soc. frang.
~lec., 7th series, 14, 92-96, (1952).
17. L. FEnRAND, "Note sur un nouveau dispositif de signalisa-
tion d'effect d'anode." (Note on a new apparatus for
signaling the anodic effect). B~dl. soc. fran~. ~lec., 14,
100, (1952).
18. L. FERRAND, "La raise en solution continue de l'alumine
dans la fabrication de l'aluminium." (Continuous dis-
solving of alumina in the manufacture of aluminum).
B~dl. soc. fran~. ~lec., 7th series, 14, 97-100 (1952).
19. T. G. PEARSON AND J. WADDINGTON.Electrode Reactions
in the Aluminous Reduction Cell. Trans. Faraday Soc.,
1, 307-320 (1947).
20. L. FERRAND,U. S. Pat. 2,061,146, Dec. 3, 1934 and 2,560,854,
July 17, 1951.
21. L. FERRAND, "Caractdristiques des dlectrolytes s faible
teneur en alumine." (Properties of electrolytes with low
alumina concentration). Bull. soc. fran~. ~lec., 7th series,
20, pp. 477-480, Aug. 1952.
22. MELLE G. SUTRAAND E. DARMOIS, "Nature de la dissocia-
tion de l'alumine dissoute dans la cryolithe fondue."
(On the nature of the dissociation of alumina in molten
cryolite). J. Phys. Radium, 97-98 (1951).
23. FRANCIS C. FRARY, "Electrolytic production of alumi-
num," J. (and Trans.) Electrochem. Soc., 94, 33 (1948).
24. F. C. FRARY, op. cit., Fig. 2, p. 35.
25. J. BOUCHARD, "l)erspectives nouvelles pour le developpe-
ment des anodes Soderberg dans la fabrication de l'alumi-
nium." (New perspectives in the development of Soder-
berg anodes in the manufacture of aluminum). Bull. soc.
franG ~lee., 7th series, 14, 101-111 (1952).