Ind. Eng. Chem. Res.

2005, 44, 6591-6598 6591

Thermal Decomposition of Aluminum Chloride Hexahydrate

M. Hartman,* O. Trnka, and O. Šolcová
Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic,
165 02 Prague 6-Suchdol, Czech Republic

The decomposition rate of aluminum chloride hexahydrate (AlCl3‚6H2O) was measured as weight
loss at ambient pressure and elevated temperatures up to 270 °C. Such incomplete thermal
decomposition produces a porous and reactive basic aluminum chloride [Al2O3‚2HCl‚2H2O or
Al2(OH)4Cl2‚H2O] which dissolves in water to give poly(aluminum chloride) used as an efficient
flocculation agent. A slowly rising temperature method and very small sample masses, which
minimize heat and mass transfer intrusions, were employed to determine intrinsic reaction rates.
A fractional order kinetic equation of Arrhenius type was proposed for the decomposition and
tested also against the results amassed by experiment in a constant temperature mode. This
correlation allows the estimation of the reaction rate as a function of temperature and the extent
of decomposition. It can be readily employed in modeling and simulation of the decomposition
process. The contents of aluminum and chlorine in the decomposed solids were also explored in
the course of the decomposition process. Pore volume (porosity), pore-size distribution, and BET
surface area data were also collected on decomposed chloride particles.

Introduction
Poly(aluminum chloride), PAC, has been known and
employed as an effective flocculating agent in water
treatment processes. The term PAC denotes an aqueous
solution of basic aluminum chloride hydrate (approxi-
mately Al2(OH)4Cl2‚H2O or Al2O3‚2HCl‚2H2O), the con-
centration of which corresponds to about 10 wt % Al2O3.
The basic aluminum chloride hydrate, BAC, is formed
by the well-controlled, partial thermal decomposition of
aluminum chloride hexahydrate (AlCl3‚6H2O) at el-
evated temperatures.1,2 Aluminum chloride hexahydrate
is produced, for instance, by the reaction of aluminum
hydroxide with an aqueous solution of hydrogen chloride
and by subsequent crystallization.
It has been well-established that anhydrous alumi-
num salts cannot be simply formed by heating the
corresponding hydrates because of their amphoteric
properties and tendency to hydrolyze. Aluminum chlo-
ride hexahydrate should be written as [Al(H2O)6]Cl3
rather than as AlCl3‚6H2O since the interaction force
Al-O prevents forming the Al-Cl bonds.
At high temperatures,3-5 the following, well-defined,
decomposition reaction takes place
1
[Al(H2O)6]Cl3(s) ) Al2O3(s) + 3HCl(g) + 4.5H2O(g)
2 (i.e., P ) 1.01325 bar), and predicted by eq 4 amounts
(A)
Its standard enthalpy, deduced from Barin’s6 ther-
modynamic data, is as large as
∆HA° (298 K) ) +996.03 kJ/mol Al2O3
Thermodynamics constraints imposed on reaction A
can be expressed by
* To whom correspondence should be addressed. Tel.: +420
220390254. Fax: +420 220920661. E-mail: hartman@icpf.cas.cz.
10.1021/ie058005y CCC: $30.25 © 2005 American Chemical Society
Published on Web 07/15/2005
25978.8
log K ) 85.342 - (1)
T
where
K ) PHCl3‚PH2O4.5 (2)
The dissociation pressure of AlCl3‚6H2O, P, is taken
as
P ) PHCl + PH2O (3)
With respect to stoichiometry it holds
PH2O ) 1.5 PHCl (3a)
and we get
3463.84
log P ) 8.07122 - (4)
T
It should be noted that eqs 1 and 4 are based upon the
thermochemical data recently compiled and tabulated
by Barin.6 The decomposition temperature, Td, defined
as a temperature at which the dissociation pressure, P,
is equal to the pressure of the surrounding atmosphere
to 429.5 K (156.3 °C).
At temperatures below 1000 °C, the less compact
γ-Al2O3 (F ) 3.40 g/cm3) is formed. It exhibits the
defective, cubic, face-centered structure. This open form
constitues the basis of the so-called active aluminum
oxide which is frequently used, for example, in catalysis,
ion exchange, and chromatography.
For the sake of PAC production,1,2 AlCl3‚6H2O as the
precursor is incompletely decomposed at about 160-200
°C under ambient pressure. In such operation condi-
tions, the exact decomposition chemistry has not been
fully understood yet. The following reaction is usually
assumed in the literature4,5 to occur
6592 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005
2[Al(H2O)6]Cl3(s) ) Al2O3‚xHCl‚yH2O(s) +
(6 - x)HCl(g) + (9 - y)H2O(g) (B)
The stoichiometric coefficients x and y are usually
presumed to be near 2. This figure (x ) y ) 2) was
employed in all stoichiometric calculations throughout
this work.
In their recent studies, Park et al.1,2 focused on the
bench-scale decomposition of aluminum chloride hexahy-
drate and the production of poly(aluminum chloride).
Little is known about the intrinsic reaction kinetics,
chemistry, and the textural features of the reaction
product.
In this article we present experimental findings on
the thermal decomposition of aluminum chloride hexahy-
drate at elevated temperatures. The purpose of the work
was to elucidate the intrinsic kinetics and the chemistry
of the decomposition reaction, and the physicochemical
properties of the reaction product.
Experimental Section
Material. The work was carried out with the alumi-
num chloride hexahydrate, ACHH, (AlCl3‚6H2O) ob-
tained from Sigma-Aldrich, with purity above 99% and
the density as large as 2.398 g/cm3. This material was
also subjected to X-ray powder diffraction analysis with
the use of a model X’Pert Philips Co. (Philips Analytical
X-ray B. V.). Results confirmed the presence of a single
solid component in the sample.
DTA and TGA curves of the employed, finely-ground
aluminum chloride hexahydrate were recorded (model
TG-750, Stanton-Redcroft Co.). As can be seen in Figure
1, there is a single, large endothermic peak on the DTA
curve at about 185-190 °C. It is believed that this
massive peak reflects a maximum rate of the formation
of the basic aluminum chloride. It should also be noted
that the decomposition reaction is strongly endothermic.
There is no discernible reason for the minuscule, but
noticeable, wave occurring at about 35 °C on the DTA
curve.
Crystals of the hexahydrate were first crushed, then
ground, and finally sieved to provide samples for the
kinetics experiments. To conform to common practice
(Mu and Perlmutter,7,8 Hartman et al.,9-12 and Kim and
Yim13), all experiments were run on finely powdered
samples with particle sizes between 50 and 80 µm.
Procedure and Apparatus. Decomposition TGA
experiments were performed with the finely powdered
samples at a constant temperature increase rate of 3
°C/min. Initial sample weights were close to 10 mg, and
air flow of 20 mL/min was maintained. Larger samples
were only employed for chemical analyses and textural
measurements. Also, constant temperature experiments
were done under such conditions. In this work, temper-
ature was maintained at a desired level within a range
of (0.1 °C. The same apparatus was employed for both
nonisothermal measurements and isothermal runs. The
TGA module monitors the weight of a sample and its
rate of change continuously, when heated in any inert
(or reactive) gas, either as a function of increasing
temperature or at a preselected temperature. The DTA
unit measures the temperature difference between a
sample and a reference.
The gas space over the sample was as large as about
70 cm3. A special arrangement (a doughnut-shaped
baffle) prevented the gas stream from bypassing the
Figure 1. DTA and thermogravimetric results (TGA) for alumi-
num chloride hexahydrate (AlCl3‚6H2O) amassed at a heating rate
of 3 °C/min between room temperature (22 °C) and 270 °C. Initial
mass of samples, 20.5 mg; flow rate of entrainer (air), 20 mL/min;
standard sample (DTA), Al2O3.
sample. Furthermore, the sample pan contained small
holes which permitted gas to flow past the sample. The
tip of the thermocouple was located about 1-2 mm
below the sample pan.
Provided that the chemistry of a decomposition reac-
tion is well-defined, thermogravimetric analysis (TGA)
offers solid data under well-controlled laboratory condi-
tions. If small samples, fine-powdered solids, and low
heating rates are used, intrusive heat and mass transfer
effects on the rate of reaction are minimized. Removal
of the gaseous product of reaction eliminates a possible
effect of equilibrium constraints.
Since the chemistry of the decomposition process of
aluminum chloride hexahydrate is not straightforward,
thermogravimetric experiments need to be supple-
mented with chemical analyses.
The extent of decomposition of the aluminum chloride
hexahydrate (ACHH) was determined as weight loss.
With respect to the uncertainties of the reaction chem-
istry, the measured weight loss was transformed into
the conversion of the chloride to the unequivocally
defined oxide (Al2O3) by means of the relationship
2 MACHH wo - w(τ)
X) ‚ ‚ (5)
z 9MH2O + 6MHCl wo
The symbols wo and w(τ) are the initial mass of the
sample and the mass of the sample at any moment of
time, respectively. The symbol z is the weight fraction
of AlCl3‚6H2O in the original (initial) reactant (z ) 0.99).
Complete conversion of AlCl3‚6H2O to Al2O3 (X ) 1)
corresponds to a relative decrease in weight of 0.78095
for z ) 0.99. Provided that this aluminum chloride
hexahydrate is completely converted into the basic
chloride [Al2(OH)4Cl2‚H2O or Al2O3‚2HCl‚2H2O], the
relative weight loss only amounts to 0.5576. The weight
loss is a directly and well-determined quantity. That is
why it accompanies in any event the data on the
conversion in this work.

Figure 2. Thermal decomposition of aluminum chloride hexahy-
drate (AlCl3‚6H2O) in a temperature-increasing experiment. Initial
mass of the sample, 14.82 mg; heating rate, 3 °C/min; flow rate of
entrainer (air 20 cm3/min; O, experimental data points. The solid
line shows the predictions of eq 6.
Results and Discussion
Nonisothermal Decomposition Kinetics. Prelimi-
nary experiments indicated that first traces of the
commencing decomposition of AlCl3‚6H2O became de-
tectable at about 90 °C. The data provided by the rising-
temperature method, some of which are plotted in
Figure 2, were employed as the practical basis for
development of a kinetics equation describing the rate
of the overall decomposition reaction. As can also be
seen in Figure 2, the decomposition of AlCl3‚6H2O
becomes quite rapid at about 150 °C.
It cannot be anticipated that a single kinetic rate
equation can describe the thermal decomposition ex-
plored in this work. In general, the decomposition of a
solid can be represented by a rate expression
dX E
dτ [
) ko exp -
RT( )]
(1 - X)n (6)
with the initial condition
X ) 0 at τ ) 0 (7)
This equation accounts for possible effects of nucle-
ation and diffusion on the rate of decomposition. It
reduces to the Jerofeev equation for n ) 1 (Mu and
Perlmutter7); it conforms to the three-dimensional and
two-dimensional shrinking core models for n ) 1/3 and
n ) 1/2, respectively. The equation follows the Avrami
nucleation law (constant density of nuclei and one-
dimensional nucleus growth) with n ) 0 (Mu and
Perlmutter;7,8 Hartman et al.14).
The experimental data from the decomposition run
were tested empirically by fitting to the linearized form
of eq 6
dX/dτ E 1
ln ) ln ko - ‚ (8)
(1 - X)n R T
Values of the reaction rate, ∆X/∆τ, were determined
from the curve X vs τ at equal conversion intervals,
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6593
thirty points were taken to fit eq 8. When the effective
order of reaction, n, was found by a trial and error
procedure, the other kinetics parameters were computed
by a least-squares method. The activation energy and
frequency factor were determined from the slope and
the ordinate intercept of the best-fit straight line,
respectively. The values of kinetic parameters inferred
from the temperature-increasing experiments amount
to
ko ) 1.61 × 1014 1/s, E ) 1.359 × 105 J/mol,
and n ) 3.56
Since the above relationship 6 is nonlinear, it is, in
general, sensitive to the variations in values of the
respective kinetics parameters. The conversions com-
puted for different times of exposure and temperatures
from eq 6 with the use of the above-mentioned kinetics
parameters are in Figure 2 compared to the correspond-
ing experimental values determined at temperatures
between 30 and 270 °C. As can be seen, the experimen-
tal data points plotted in this figure fit the computed
curve fairly well.
Park et al.1,2 assumed that the decomposition reaction
is first-order in conversion of the chloride (i.e., n ) 1)
and fitted their laboratory-scale data to the integrated
form of eq 6
ln [
-ln(1 - X)
τ ] E 1
) ln ko - ‚
R T
(9)
n)1
From the straight line drawn to fit the data amassed
at 160, 180, and 200 °C, the authors1,2 calculated the
preexponential factor, ko, and the activation energy, Eo,
to be as large as 297.6 1/s and 5.55 × 104 J/mol,
respectively. The authors warn that the decomposition
is too slow still at 140 °C and eq 9 may not be applicable
at such temperatures.
Isothermal Decomposition Kinetics. The rate of
thermal decomposition of the aluminum chloride hexahy-
drate was also explored in the constant temperature
mode. The constant temperature runs were carried out
in the range 90-150 °C. Preliminary tests proved that
the particles did not melt at such temperatures. The
results of constant temperature runs are shown in
Figure 3. As can be seen, there is an appreciable
difference in the course of the curves measured at 90-
110 °C and those obtained at 130-150 °C. While the
first three lines are nearly linear, the other three exhibit
a sigmoid shape. In accordance with the temperature-
increasing experiments, the decomposition becomes
quite rapid at about 140 °C. It should be noticed that
in the range 130-150 °C, the experimental curves level
off after about 2 h exposure. Also, the weight loss,
attained after such a long exposure, slightly augments
with the increasing temperature.
In Figure 3 are also presented the predictions of eq 6
for 140 °C with the use of the kinetics parameters
deduced from the results obtained by the nonisothermal
procedure. As can be seen, agreement between the
constant temperature results and the predictions ap-
pears to be reasonable.
The different modes of experiment seem to be among
major factors affecting differences between experiment
and the predictions in Figure 3. It is a common experi-
ence that the results of the temperature-increasing runs
6594 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005
Figure 3. Thermal decomposition of aluminum chloride hexahy-
drate (AlCl3‚6H2O) in temperature-constant experiments. Initial
mass of the samples, 14.45-15.86 mg; flow rate of entrainer (air),
20 cm3/min. The solid lines represent the experimental curves; O,
predictions for the temperature 140 °C of eq 6, the parameters of
which were deduced from the temperature-increasing run.
are notoriously sensitive to the rates of heating. Heat
transfer can affect the results provided by constant
temperature runs, particularly if the rapid rate of
decomposition is coupled with the high heat of reaction.
Considerable sensitivity of the rate of reaction to tem-
perature also should not be overlooked. In light of such
facts the found differences seem to be understandable.
It is believed that the proposed kinetic equation can be
applied to modeling and simulation of suitable reactors
for the thermal decomposition of aluminum chloride
hexahydrate. The empirical relationship developed in
this work has usual limitations and it should be applied
with caution outside the experimental conditions from
which it was deduced.
Decomposition of Larger Samples. To secure
quantities of partially decomposed aluminum chloride
hexahydrate needed for chemical and textural analyses,
larger samples of the chloride were exposed to elevated
temperatures. Crystals of the chloride were crushed and
sieved, and the fraction of particles within a sieve size
range of 0.50-0.63 mm (d h p ) 0.565 mm) was investi-
gated in this segment of the work. Samples (3 g),
dispersed in shallow corundum crucibles, were inserted
into a muffle furnace and exposed to the stream of air
as a sweep gas at the temperature of interest (150-
350 °C) for 60 min. Then the decomposed particles were
stored in airtight containers, and shortly afterward they
were subjected to chemical and textural analyses. The
weight loss of each sample was also determined and is
shown in Figure 4.
For the sake of comparison, some data read from the
TGA lines shown in Figure 3 are plotted along with the
new decomposition results. As can be seen, the new
decomposition curve outlined by the data amassed with
the larger samples is distinctly shifted (30-80 °C)
toward higher temperatures. The collected data also
suggest that even at the highest temperature employed
(350 °C), the complete conversion to Al2O3 had not yrt
been attained.
Park et al.1 explored the extent of decomposition of
AlCl3‚6H2O at different temperatures (140-200 °C)
using 5-g samples placed in a small flask which was
Figure 4. Thermal decomposition of larger samples of aluminum
chloride hexahydrate in a muffle furnace. Initial mass of the
samples, 3.002-3.006 g; flow rate of entrainer (air), 50 cm3/min;
elapsed time of exposure, τ ) 60 min; O, this work, decomposition
in a muffle furnace; ×, this work, deduced from the TGA data
shown in Figure 3; b, results of Park et al.1
immersed into a heated silicon oil bath. Some results
deduced from the authors’ experimental curves are also
incorporated into Figure 4.
As can be seen in this figure, Park’s data are not in
conflict with the trend of our experimental findings.
Amounts of Aluminum and Chlorine in the
Partially Decomposed Solids. A natural question
arises as to continuous changes in the solids composition
in the course of the decomposition process. As apparent,
the composition of the evolved gas inherently unfolds
from the progress of the decomposition reactions occur-
ring within the particles.
The chloride particles, first exposed to different tem-
peratures (150-350 °C) and to the sweep gas for 60 min
in the muffle furnace, were then analyzed for aluminum
and chlorine. The measured contents of aluminum
increased from 12.4 to 44.2 wt %; those of chlorine
decreased from 43.2 to 8.9 wt % as the relative weight
loss increased from 13.2 to 75.5%. These values of
weight loss correspond to the extents of decomposition
of 16.7 and 95.7%, respectively. The determined mass
fractions of both species are shown in Figure 5 in
dependence on the fractional weight loss.
The chlorine curve in Figure 5 indicates that hydro-
gen chloride commences liberating at very early stages
of the decomposition reaction. Both curves in Figure 5
become quite steep when the decomposition is nearing
completion.
As illustrated in Figure 6, the relationship between
the content of aluminum and that of chlorine in the
decomposing solids is nearly a linear one. The depen-
dence of the molar ratio of Cl to Al in the solids on
weight loss shown in Figure 7 exhibits a slightly concave
shape.
Textural Features of the Decomposed Particles.
In the course of the decomposition, water vapor and
hydrogen chloride are evolved and consequently numer-
ous pores are formed. Upon the loss of gases, the
pseudomorphs similar to the parent chloride tend to
remain at lower temperatures.15 At higher temperatures
recrystallization or sintering of the reaction product
takes place.

Figure 5. Amounts of aluminum (Al) and chlorine (Cl) in the
partially decomposed samples as functions of weight loss of the
solids. Experimental conditions are the same as those mentioned
in the caption for Figure 4.
Figure 6. Relationship between the weight fractions of aluminum
(Al) and chlorine (Cl) in the partially decomposed solids. Experi-
mental conditions are the same as those mentioned in the caption
for Figure 4.
At first, an effort was taken to explore how the volume
of the solid phase is changed by the decomposition
process. Since the operation temperatures are not high,
it is feasible to assume that no shrinkage occurs and
the decomposed particle retains its gross external
volume. As considerable amounts of gases (water vapor
and hydrogen chloride) are evolved in the course of the
reaction, it is evident that the porosity/pore volume of
the decomposing particle is increased as the decomposi-
tion advances. It should be noted, however, that the
reaction product is not unambiguously defined. There-
fore, an analytical relationship cannot be developed
between the porosity of the decomposing particle and
the progress of decomposition.16,17
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6595
Figure 7. Molar ratio of chlorine (Cl) to aluminum (Al) present
in the partially decomposed solids as a function of the fractional
weight loss. Experimental conditions are the same as those
mentioned in the caption for Figure 4.
Figure 8. True particle density (FHe) and particle density (FHg)
as functions of fractional weight loss. Experimental conditions are
the same as those mentioned in the caption for Figure 4.
True and particle density of the decomposed products
were determined by helium and mercury pycnometry,
respectively. Pore-size distributions were determined by
measuring the volume of mercury penetrating the pore
volume at increasing pressure.
Figure 8 shows the results of the pycnometric mea-
surements in dependence on the extent of decomposi-
tion. It is obvious that the measured true densities
increase with increasing extent of decomposition. Nev-
ertheless, all values (1.64-1.95 g/cm3) are much lower
than the density of γ-Al2O3, which amounts to 3.40
g/cm3. This fact suggests that some pseudomorphous
6596 Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005
Figure 9. Dependence of the porosity of decomposed particles on
the extent of decomposition. Experimental conditions are the same
as those mentioned in the caption for Figure 6.
Figure 10. Differential pore-size distribution of the particles
decomposed at 150 °C. Time of exposure, 60 min.
structures can form and persist at the employed tem-
peratures.
The curved line shown in Figure 9 displays how the
porosity (pore volume) augments with the increasing
extent of decomposition. The highest porosity deter-
mined with the particles decomposed at 350 °C amounted
to 57%. With increase in the porosity of BAC its rate of
dissolution in water will most likely increase. The BET
surface area of the decomposed particles was on the
order of 101 m2/g.
The pore size distributions of the solids decomposed
at 150, 250, and 350 °C were also determined. The
amassed results are illustrated in Figures 10, 11, and
12. The measured curves indicate that the radii of pores
are distributed over the 1-104 nm range. The derivative
curves shown in these figures exhibit their peaks at the
radii of 20, 300, and 400 nm as the most probable pore
Figure 11. Differential pore-size distribution of the particles
decomposed at 250 °C. Time of exposure, 60 min.
Figure 12. Differential pore-size distribution of the particles
decomposed at 350 °C. Time of exposure, 60 min.
sizes in the respective samples. The shift of the most
probable pores to larger ones with the increasing
temperature of decomposition is most likely linked to
sintering or recrystallization of the formed pseudomor-
phs similar to the parent chloride. The bimodal distri-
bution displayed in Figure 11, with the second maxi-
mum at about 1000 nm, was only found at 250 °C.
Conclusions
Both water vapor and hydrogen chloride are released
when aluminum chloride hexahydrate is gradually
heated. First noticeable signs of the thermal decomposi-
tion of the chloride occur at 90 °C.
The results provided by the nonisothermal method
showed that the reaction kinetics was more than third-
order in mass of the chloride up to high extents of
decomposition. A reaction rate equation educed from
these temperature-increasing thermogravimetric data
describes the course of decomposition with fair accuracy.

The results of the isothermal experiments exploring the
extent of the decomposition reaction are in reasonable
accordance with the predictions of the proposed ki-
netic relationship based upon the rising-temperature
data.
The amount of chlorine in the decomposing particles
commences decreasing from very early stages of the
decomposition process. Thus, the chloride particles
decomposed at 350 °C for 60 min still contained 8.9%
Cl by weight.
Original, dense crystals of the chloride become porous
as their decomposition proceeds. The largest measured
porosity amounted to 57% (0.63 cm3/g). The true density
of decomposed solid slowly increases with the extent of
decomposition from 1.65 to 1.95 g/cm3. The particle
(apparent) density, needed for fluidization calcula-
tions,18 decreased with the progress of reaction from 1.3
to 0.82 g/cm3.
The pore-size distributions of the decomposed samples
indicate that the radii of pores are distributed over the
1-104 nm range. The most probable pore size in the
solids increased from 20 to 400 nm in dependence on
the extent of decomposition.
Acknowledgment
This research was supported by Grant 203/02/0002
from the Grant Agency ČR. The authors thank Mrs. H.
Součková and Mrs. H. Šnajdaufová for the textural
measurements. Assistance of Mrs. E. Macháčková and
Mr. J. Horáček in the chemical analyses is also appreci-
ated.
Nomenclature
Abbreviations
ACHH ) aluminum chloride hexahydrate, AlCl3‚6H2O
BAC ) basic aluminum chloride, Al2(OH)4Cl2‚H2O or Al2O3‚
2HCl‚2H2O
PAC ) Poly(aluminum chloride); basic aluminum chloride
dissolved in water
Symbols
∆HA° (298 K) ) standard enthalpy of reaction A at 298.15
K, kJ/mol
∆w ) (weight) mass loss [) wo - w(τ)], g
∆w/wo ) relative (weight) mass loss
h p ) average particle size determined by sieving, mm
d ganic Sulfates and Their Hydrates. Ind. Eng. Chem. Process Des.
e ) fractional porosity of solid ) (FHe - FHg)/FHe ) (VpFHe)/
(1 + VpFHe) ) VpFHg
E ) effective (apparent) activation energy, fitted param-
eter, J/mol
ko ) preexponential factor, Arrhenius constant, fitted
parameter, 1/s
K ) quantity defined by eq 2, bar7.5
ln ) base-e, natural (Napierian) logarithm ) 2.30259 log
log ) base-ten (Briggsian) logarithm ) 0.434294 ln
Mi ) molar mass of species (MH2O ) 18.015; MHCl ) 36.461;
MAlCl3‚6H2O ) 241.431; MAl2O3‚2HCl‚2H2O ) 210.913; MAl2O3 )
101.961; g/mol
n ) effective (apparent) order of reaction, fitted parameter
ni ) amount of species “i”, mol
P ) dissociation pressure given by eq 3, bar
PHCl ) partial pressure of HCl, bar
PH2O ) partial pressure of water vapor, bar
r ) pore radius, nm
rp ) radius of pore, nm
R ) ideal gas-law constant ) 8.31441, J/(mol K)
Ind. Eng. Chem. Res., Vol. 44, No. 17, 2005 6597
t ) Celsius temperature, °C
T ) thermodynamic temperature, K
Vp ) pore volume ) (1/FHg) - (1/FHe) ) [e/(1 - e)]‚(1/FHe) )
e/FHg, cm3/g
wo ) initial (original) mass of sample (τ ) 0), g
w(τ) ) mass of sample of any moment of time τ, g
X ) fractional extent of decomposition of aluminum
chloride hexahydrate (AlCl3‚6H2O) expressed as the
fractional conversion of the chloride to aluminum oxide
(Al2O3) given by eq 5
z ) mass fraction of species (AlCl3‚6H2O) in original
reactant
zi ) mass fraction of species “i” in solids
Greek Letters
F ) solid density, g/cm3, kg/m3
FHe ) skeletal, true (helium) solid density, g/cm3, kg/m3
FHg ) particle, bulk, apparent (mercury) solid density,
g/cm3, kg/m3
τ ) exposure time, s, min
Subscripts
Cl ) chloride(s), (Cl-)
Al ) aluminum (Al)
i ) species “i”
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Received for review January 3, 2005
Revised manuscript received May 2, 2005
Accepted June 12, 2005
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