Equilibrium of the 2Al (1) + AICI,(g) = 3AICI (g) Reaction
in the Subhalide Process of Aluminium
(Study of Extractive Metallurgy of Aluminium (I)
By Takeaki Kikuchi", Toshio Kurosawa* and Testuo Yagihashi*
Equilibrium constants of a fundamental reaction of the aluminium subhalide process, 2AK(1)-+AICh(g) =
BAICI (g), wore dotermined by the low method using argon carrier between 1000°C and 1250°C. As @ result of
‘this experiment, equilibrium constants and standard free energy were obtained by the following equation:
log K,(~ PPAICYP AICI) — ~14,440/7 + 9.87
40%; 66,060 — 45.167
‘The heat of formation and entropy of AICI{g) obtained from the experimental data and other thermodynamic
‘values were -22,250 cal/mol and 48.7 cal/mol respectively. By the use of the equilibrium constants, the
reaction ratio of aluminium trichloride was calculated at a reduced pressure and in argon carrier, respectively.
(ceived march
I. Introduction
Aluminium is produced by means of the fused salt
electrolysis using alumina obtained mainly from rela-
tively higher grade bauxite. However, another
extraction method called the Gross or subbalide process
hhas recently been investigated, and some technological
or industrialization reports have already been
published.
In this process, crude aluminium alloy is produced
by reduction of alumina bearing ores with carbonaceous
reducing material such as coke or charcoal in. the
first. step, and then aluminium trichloride gus is
‘passed over the alloy heated at high temperature to
form aluminium monochloride, and finally pure
aluminium ean be redeposited when monocbloride is
cooled.
This process has a characteristic in the utilization
‘of subchloride of aluminium monochloride, and it
will be significant if this process is developed industri-
ally. Several reports have been published in regard
to the fundamental reaction of this process, viz.
aluminium monochloride formation by the reaction of
aluminium with aluminium trichloride, but consider-
able differences can be observed in the results,
‘Therefore, equilibrium constants of this reaction
‘were measured by the flow method in order to obtain
reasonable values. Moreover, some thermodynami
relations concerning the subhalide process were
evaluated from the obtained values,
II, Experimental Apparatus and Procedure
For the purpose of obtaining equilibrium constants,
‘the spectral method measuring the absorption
intensity of formed aluminium monoehloride and the
flow method" determining the reacted aluminium
* ‘Notional Rosarch Institute for Metals, Tokyo, Japan,
(1) LM. Foster, AS. Rusll & CN. Cochran: J. Amer
Chom. Soo, 72 (1950), 2580,
(2) M. Heise, K. Wieland: Helvetien Chemica Acta,
34 (1951), 2182.
‘Trans. JIM
vse)
trichloride supplied to the reaction zone were applied
previously. In this investigation, the latter method
‘was selected to obtain the equilibrium constants.
1. Experimental apparatus
‘The apparatus used in this experiment is shown by
the schematic diagram in Fig. 1. The apparatus con-
sists of an argon purifier, aluminium trichloride evapora-
tor, reaction tube, and condensing tube of aluminium
trichloride gas. Argon in a bomb was purified and
measured by passing through concentrated sulphu
acid, calcium chloride, soda lime, phosphorus pentoxide
‘and magnesium chip heated at 400°C. After then, it
was fed to the aluminium trichloride evaporator
through a liquid paraffin flow meter.
‘The evaporator constructed by transparent quartz
tubing was immersed in a silicone oil thermostat, and
heated. properly below 180°C, namely, the sublimation
point of aluminium trichloride, “Evaporated alu-
minium trichloride gas was carried into the reaction
tube by argon,
The reaction tube consisted of a quartz tube of
800 mm. long and 40mm in inner diameter sheathed
internally with a high grade graphite liner (32mm in
inner diameter, 500 mm in length), and silica wool was
packed between the tube and the liner.
The reaction tube was heated in a Siliconit furnace
where the temperature was maintained within:=5°C
at 1100°C in the Sem range. A calibrated Pt-PtRh
thermocouple was set upon the surface of the reaction
CS. Compbell, PLC. Kent & Dib. Levi
A General Discussion on the Physical Chemistry of
Procoss metallurgy, (1948), 206.
(® P. Weiss: Z. Erabergbon u, Motallhittenwesen, 3
(1950), 241.
(5) KE. Martin, AS. Russell, & CN. Cochran: J. Amer.
Chem. Soe., 73 (1951), 1466.
(®) Shimizn, Uchida, Oikawa & Ito: Keikinzoku, 20
(1950), 8,
(1) Morinaga & ‘Takahashi:
Spring Meoting Lecture.
Denki Kagalcukai, 1963,
1964 Vol. 5 Equilibrium of the 241 ()-+AICE,~ 3AICI(g) Reaction in the Subhalide Process of Aluminium
133
Fig, 1 Experimental spparatus for determination of equilibrium constants by the flow method.
+ Angon bomb
Cone. sulphuric acid
: Calelum chloride
Sona lime
: Phosphorus pentoxide
+: Flow metar
Nichrome furnace
Magnesium chip
ESTES ORE
2
5
‘tube just above the position of the inserted aluminium,
boat, but no temperature difference was found between
the inner and outer positions of the reaction tube.
‘Aluminium trichloride decomposed from monochloride
and unreacted trichloride were removed from another
outlet, and condensed in the trap cooled with dry ice-
alcohol.
2. Sample and measuring method
Aluminium and aluminium trichloride used in this
experiment were of high purity, Aluminium had a
purity of 99.9295 and it contained 0.039% Si, 0.0595
‘Fe, and0,00595 Cu, asimpurities. Aluminium triehloride
synthesized by reaction of aluminium with chlorine
‘was distilled and then sealed off into the evaporator
fas fast as possible. Prior to the run, the evaporator
‘was connected with the reaction tube.
In order to maintain a high purity of aluminium
alumina boats of 98.8~99.29 Al,0, and 0.3~0.49%
SiO, were used. The boat was made to fit the graphite
liner, and it was semieylindrical, 12 mm in height, 23
mm in width and 70 mm in length and 2 mm in thick-
ness. To obtain a nearly constant surface area, alum-
{nium weighing 15~18 was used in all experiments,
‘The measuring procedure was carried out in the
following way. ‘The aluminium chip was set in the
boat, and it was inserted in the reaction tube. ‘Then
the aluminium trichloride evaporator was connected
with one side of the reaction tube by the ball joint.
‘The amount of aluminium trichloride in the evaporator
was 100~150g. After closing a cock of the evaporator
the whole system was evacuated and the leakage
condition was then checked by the mercury man-
cometer. During this process, the aluminium trichloride
evaporator was cooled in a dry ice-aleohol bath to
prevent sublimation of aluminium trichloride. In
the next place argon was delivered into the whole
system, and the reaction tube was heated rapidly
Js AICL, evaporator
K: Nichrome ribbon heater
LL: Siliconit farance
-M: Sill reaction tube
N: Graphite tube
0: Glass shieled
P: AICI, condensing vessel
Q: Pure aluminium
until it became constant at a desired temperature. Then
the aluminium trichloride evaporator was immersed
in a silicone oil bath held at a proper temperature.
As evolution of aluminium trichloride gas was
cecurred after one minute of immersion, this was
chosen as the starting time of the flow method. Argon
‘was delivered into the evaporator at a predetermined
flow rate, and the resultant gas mixture was supplied,
to the reaction zone. The flow rate of argon was
Sec/min, 20cc/min, and 40ce/min respectively, and
aluminium trichloride evaporation was controlled by
‘means of argon flow and bath temperature, "The reac-
tion time was 2~3 hr, but a longer reaction was con-
ducted in the case of low reaction temperature and
slow argon flow in order to obtain a more-aceurate
result. ‘The reaction temperatures were 1000°, 1100°,
1200" and 1250°C.
Aluminium trichloride delivered into the reaction
zone reacted with aluminium heated in the uniform
temperature range, and aluminium monochloride
formed in the hot zone was decomposed into metallic
aluminium and trichloride in the lower temperature
Aluminium was deposited in the form of small
particles on the surface of the graphite liner. After
the lapse of a predetermined time, the silicone oil
bath was removed out of the evaporator rapidly, and
cooled by dry ice-aleohol trap to cease the evolution
of aluminium trichloride. Moreover, the reaction
‘tube was cooled by an electric fan. ‘Then amounts of
the evaporated aluminium trichloride and transported
aluminium were measured, and the equilibrium con-
stants were obtained from the reaction ratio of alum-
num. trichloride.
IIL. Experimental Rresult and Consideration
1. Calculation method of equilibrium constants
and experimental results
‘The subhalide reaction may be denoted by the at
following equation according to the spectral. studies
carried by Bhaduri, et al.@) and Foster ot al.
2Al (I) + AICI, (g) = SAICL().
Equilibrium constant K, of the above reaction is
described by the use of partial pressures, Paci, Paici
and activity of aluminium denoted by asi
Ky = PualPacy tn «
To obtain these partial pressures, the reaction ratio
of aluminium trichloride can be written in the follow-
ing relation
(transported Al(g)/supplied AICI,(g)) 183.35)
53.96.
If the total pressure at equilibrium, mols of alum-
injum trichloride and argon supplied during the reac-
tion are taken to be P, a, b respectively, then mols of
trichloride, monochloride and argon can be denoted
by a(1-a), 3aa, b respectively, and the total of mols
may be represented as a (1+2a)-+5.
‘Therefore, partial pressures of Pacis and Pay ate
Pascy= Pa (1—a)fa (1+22) + 8
Pascr = 8 Paala(1+2a) +b.
Inserting these relations into the above Ky
equation, and combining P and aa: taken as unity
due to atmospheric pressure and pure aluminium, the
equilibrium constants can be expressed as follows:
Ky = 2 at|(1—a) (1420+Bja) «
If constant b/a can be obtained in the gas mixture,
the true equilibrium constants may be determined
fat each temperature by extrapolation of the low
total gas flow rate. Although BJa was difficult to be
made constant under the test conditions, constant
Yfa could be obtained by using the following method,
Figs. 2~5 show a logarithm of apparent, equilibrium
constants, log K,’, on the ordinate and the alum-
inium trichloride flow rate on the abscissa for a range
of argon flows and temperatures, and the straight lines
are drawn by least squares at each angon flow rate.
For example, when a definite condition for bJa=1/3
is sought from Fig. 2, the following result can be
ro00"e + £00184 ms/ne A
‘sec/mins
6 :00586m/a
"aoce/ mia)
‘Ely FLOW RATE (mot7avea/nr)—“imol/ard
Mig. 2 Relation between the logasithm of apparent
‘equilibrium constants and the AICI, flow rate
‘st 100°C.
(8) BN. Bhaduri & A. Fowler: Proc, Roy. Soc, A145
(198, 321
Taksaki Kikuchi, Toshio Kurosawa and Teatuo Yagihashi
‘score
2 s00sscine) nee
‘aoce” wnt
© so1orema! nen
\aoee/ain
Sea RTE ane
Fig. 3 Relation botween th logarithm of apparent
crv constant and the AIG, flow rate
st hove
04 naira
teem
©: o1oreeni/nea
taoce ate)
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