Article No : a01_527

Aluminum Compounds, Inorganic

OTTO HELMBOLDT, Giulini Chemie GmbH, Ludwigshafen, Germany
L. KEITH HUDSON, Aluminum Company of America, Alcoa Center, Pennsylvania, USA
CHANAKYA MISRA, Aluminum Company of America, Alcoa Center, Pennsylvania, USA
KARL WEFERS, Aluminum Company of America, Alcoa Center, Pennsylvania, USA
WOLFGANG HECK, BASF Aktiengesellschaft, Ludwigshafen, Germany
HANS STARK, BASF Aktiengesellschaft, Ludwigshafen, Germany
MAX DANNER, Hoechst Aktiengesellschaft, Werk Gersthofen, Augsburg, Germany
NORBERT R€oSCH, Clariant Produkte (Deutschland) GmbH, Gersthofen, Germany

1. Aluminum Sulfate and Alums . . . ..... . . 569 3. Aluminum Alkoxides. . . . . . . . . . . . . . . . . 578

1.1. Aluminum Sulfate . . . . . . . . . . . . ..... . . .569 4. Aluminum Chloride . . . . . . . . . . . . . . . . . 578
1.1.1. Properties . . . . . . . . . . . . . . . . . . . ..... . . .569 4.1. Anhydrous Aluminum Chloride . . . . . . . . .578
1.1.2. Production . . . . . . . . . . . . . . . . . . ..... . . .570 4.1.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . . .578
1.1.3. Uses . . . . . . . . . . . . . . . . . . . . . . . ..... . . .572 4.1.2. Production . . . . . . . . . . . . . . . . . . . . . . . . . .579
1.2. Alums . . . . . . . . . . . . . . . . . . . . . ..... . . .573 4.1.3. Quality Specifications and Analysis . . . . . . . .579
1.2.1. Potassium Aluminum Sulfate. . . . . ..... . . .574 4.1.4. Handling, Storage, and Transportation . . . . . .580
1.2.2. Ammonium Aluminum Sulfate . . . ..... . . .575 4.1.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .580
1.2.3. Sodium Aluminum Sulfate . . . . . . ..... . . .576 4.2. Aluminum Chloride Hexahydrate . . . . . . . .580
2. Aluminates . . . . . . . . . . . . . . . . . ..... . . 576 4.3. Basic Aluminum Chlorides . . . . . . . . . . . . .581
2.1. Sodium Aluminate. . . . . . . . . . . . ..... . . .576 5. Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . 583
2.2. Barium Aluminates . . . . . . . . . . . ..... . . .577 References . . . . . . . . . . . . . . . . . . . . . . . . . 583

1. Aluminum Sulfate and Alums
1.1. Aluminum Sulfate
Aluminum sulfate is the second most important
industrial compound of aluminum, after alumi-
num oxide. Aluminum sulfate was first used in
Paris in 1844 to replace potassium alum. Today,
it has taken over almost all areas of application
that potassium alum originally had.
1.1.1. Properties
Aluminum sulfate is almost insoluble in anhy-
drous alcohol but readily soluble in water; aque-
ous solutions are acidic. Literature data on solu-
bility and the structure of the precipitate in water
differ markedly and should be used with caution
(see Table 1). Previously, Al2(SO4)3
18 H2O
was thought to crystallize from aqueous solution
under normal conditions (20  C, 1 bar). This is
now doubted, because such factors as hydrolysis,
oversaturation, shifts in equilibrium, and, partic-
ularly, poor crystal formation make definitive
characterization difficult [5]. The common form
of aluminum sulfate, generally considered to be
Al2(SO4)3
18 H2O [7784-31-8], occurs in na-
ture as alunogen (hair salt) and can be crystal-
lized from hydrochloric acid solution as micro-
scopically small, white needles. However, some
researchers ascribe a hydrate water content of
17 mol to this form of aluminum sulfate [6]. A
hydrate containing 27 mol of water can be pre-
pared readily and in high purity [1]. Other well-
defined aluminum sulfates contain 16, 10, and
6 mol of water. A total of 39 basic and 3 acidic
aluminum sulfates, as well as 13 different hydrates

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a01_527.pub2
570 Aluminum Compounds, Inorganic
Table 1. Solubility of aluminum sulfate as a function of temperature (grams of anhydrous salt per 100 g water)
t,  C 0 10 20 30 40
31.3 33.5 36.15 40.36 45.73
31.2 33.5 36.4 40.4 46.1
27.5 27.6 28.0 28.8
23.9 25.0 26.9 31.5
of the neutral salt, are described in the literature
[7]. The existence of aluminum sulfates with 14,
13, 12, 9, 7, 4, 2, and 1 mol of water can be
concluded from the vapor-pressure curves and the
dehydration curves of the Al2(SO4)3 – H2O and
Al2(SO4)3 – Al(OH)3 – H2O systems [8, 9].
In industrial practice, the hydrate water con-
tent is unimportant because ‘‘crystalline’’ alumi-
num sulfate is a ground, microcrystalline solid
with variable water content, which is obtained
from a melt. The desired Al2O3 content is adjust-
ed within certain limits by heating. At a temper-
ature above 340  C, anhydrous aluminum sulfate
[10043-01-3] is formed, a white powder, r 2.71
g/cm3, that decomposes above 770  C to alumi-
num oxide [9].
1.1.2. Production
In Germany and most European countries, alu-
minum sulfate is produced on a large scale only
from aluminum hydroxide and sulfuric acid by
the Giulini process. In this process, aluminum
sulfate is obtained relatively easily with high
purity. Production by the action of sulfuric acid
on aluminum-containing ores (clays and bauxite
with high silicon and low iron content, e.g.,
bauxite with SiO2 > 5 %, Fe2O3 ca. 1 %) is still
important in some countries.
Giulini Process [10]. The Giulini method
for producing various grades of aluminum sul-
fate, containing between 8 and 23 % Al2O3, is
shown schematically in Figure 1.
A pressure-resistant, stirred vessel (a) is filled
with aluminum hydroxide (moist or dry). The
calculated quantity of warm sulfuric acid is
added from a preheater, and the mixture is stirred.
In calculating the sulfuric acid concentration
required to obtain an SO3 content of ca. 1 %
below stoichiometric, all process steps involving
the introduction or the removal of water must be
Vol. 2
50 60 70 80 90 100 Reference
52.13 59.10 66.23 73.14 80.83 89.11 [1]
52.2 59.2 66.1 73.0 80.0 89.0 [2]
29.9 31.0 32.8 36.6 38.74 46.85 [3]
36.4 41.7 47.0 [4]
accounted for. Generally, acid of density 1.6 g/cm3
is used. The reaction starts after 60 – 300 s and is
complete after 10 – 12 min. The heat of reaction
causes the temperature to rise to ca. 170  C, while
the pressure rises to 5 – 6 bar. The mixture must
not be stirred for more than 1 h because otherwise
the aluminum sulfate can hydrolyze to give insol-
uble basic aluminum sulfate and strongly acidic
sulfate melt. An autoclave unit allowing batches of
2.5 t can produce ca. 50 t of aluminum sulfate in a
10-h shift.
The melt is led into a copper container where it
is concentrated by flash evaporation (b). From the
evaporator, the melt is sucked into a well-isolated
vacuum tank (c), which is evacuated to the vapor
pressure of the aluminum sulfate melt. This
vacuum cooling avoids incrustation of the heat
exchanger surfaces.
The melt falls from the vacuum container into
the mixer, where it is seeded at 85  C with 1 –
2 % aluminum sulfate powder. The pulplike
product reaches the ‘‘crystallization belt,’’ a
smooth, heat-resistant, trough-form rubber con-
veyor belt (e), and crystallizes there in ca.
30 min. Because of the high heat of crystalliza-
tion, the material has a temperature of ca. 90  C
and cannot be broken to fine size in one step (f). It
passes over air-cooled conveyor belts until it has
cooled to 40  C, after which it is ground (h) and
sieved (i). The goods are filled (j) into paper or
jute sacks or transported loose in silo cars. Alu-
minum sulfate with 17.2 % Al2O3 produced in
this way contains only 0.01 % insoluble material;
therefore, digestion of the aluminum hydroxide
is almost complete. For transportation as a solu-
tion the Al2O3 content is adjusted to ca. 8 % to
avoid crystallization during transport.
Production from Bauxite. Finely ground
bauxite (for example, 60 % Al2O3, 1.5 % Fe2O3,
1.6 % TiO2, 3.0 % SiO2, 32 % H2O) also can be
used as starting material. In this case, 3 mol
H2SO4 are charged onto 1 mol Al2O3. The Fe2O3
Vol. 2
Figure 1. Production of aluminum sulfate by the Giulini process [10]
component in bauxite is disregarded because the
Al2O3 is only 97 – 98 % digested and therefore
sufficient sulfuric acid is available for production
of aluminum sulfate containing 17.5 % Al2O3.
The aluminum sulfate obtained by digestion of
bauxite contains ca. 0.5 % Fe2O3 and ca. 2.2 %
insoluble residue.
Production from Less Pure Starting
Materials. Acid digestion of predominately
silicon-rich raw materials gives a solution of
aluminum sulfate. The purity depends on the
process and starting materials. Iron, which
strongly interferes, is precipitated with calcium
Aluminum Compounds, Inorganic 571
hexacyanoferrate (II) as Berlin blue (iron hex-
acyanoferrate (II)), with calcium sulfide as iron
sulfide, or by hydrolysis as basic iron sulfate. For
details, see [11]. The clear solution is decanted
and sold as a liquid or concentrated to 61.5  B
e,
allowed to solidify, and milled. The final product,
which contains ca. 0.5 % Fe2O3 and 0.1 % insol-
uble material, is the technical grade. In addition,
there is an iron-free grade having an Fe2O3
content of ca. 0.005 %.
The Kretzschmar process is used to produce
very pure, iron-free aluminum sulfate by diges-
tion of clay (for example, 40 – 43 % Al2O3,
53 – 56 % SiO2, 2 – 4 % Fe2O3) with sulfuric
572 Aluminum Compounds, Inorganic
acid. The greater part of the impurities is re-
moved and crystals are separated from the solu-
tion by stirring. The formation of colloids is
avoided by using vacuum apparatus. Pure, large
crystals of Al2(SO4)3
18 H2O (15.3 % Al2O3)
can be separated easily from the impure mother
liquor by centrifuging [12]. The residue from the
digestion process (SiO2) can be converted with
lime to calcium hydrosilicate, which increases
the hardness of and also plasticizes lime mortar.
In a process developed by the U.S. Bureau of
Mines, alcohol is used to reduce the viscosity
of the oversaturated aluminum sulfate mother
liquor [13].
Olin Mathieson Chemical Corp. developed an
economical process for producing high-quality
aluminum sulfate from the clay or waste shale of
coal mines. Large crystals (1.5 – 3 mm) with
iron contents of less than 0.03 % are produced
in a patented crystallizer [14]. A process for
producing aluminum sulfate from alum-contain-
ing ores is given in [15].
Aluminum sulfate is produced from waste
‘‘red mud’’ (from the aluminum oxide industry)
by suspending the mud in water and passing
sulfur dioxide through the suspension until pH 2
is reached. After filtration and removal of the
sulfur dioxide in vacuo to give a pH of 4.5 – 5.0,
Al(OH)SO3 and SiO2
n H2O precipitate. The
precipitate is filtered and treated with sulfuric
acid, whereby aluminum sulfate dissolves. [16].
Commercial Grades. Whereas Al2(SO4)3

18 H2O theoretically contains 15.3 % Al2O3,
commercial grades of aluminum sulfate contain
14 – 15 %, 15 – 16 %, 17 – 18 %, 18 %, or 22 –
23 % Al2O3 (Table 2). Generally, the aluminum
sulfate containing 17 – 18 % Al2O3 (water-solu-
ble aluminum content, calculated as Al2O3) is
used most frequently. The calculated hydrate
water content of this aluminum sulfate is 13 mol.
The commercial grade containing 17 – 18 %
Table 2. Commercial grades of aluminum sulfate
Grade Al2O3, wt % Fe2O3, wt %
8 % (solution) 8 0.004
14 – 15 % 14 – 15 0.006 – 0.008
15 – 16 % 15.1 – 16.0 0.006 – 0.008
17 – 18 % ca. 17.2 < 0.01
18 % ca. 18.0 < 0.01
22 – 23 % ca. 22.8 < 0.02
*
Defined in text
Vol. 2
Al2O3 is delivered also with various special
qualities, such as low arsenic or low iron content.
The basicity of the product is defined as the
excess in Al2O3 over the stoichiometric SO3 :
Al2O3 ratio. The 17 – 18 % Al2O3 grade has a
basicity of 0.1 – 1 %, i.e., the Al2O3 content
exceeds the stoichiometric amount by 0.1 –
1 %. Occasionally, the term ‘‘basicity’’ is defined
as the ratio % SO3 to % Al2O3. For commercial
aluminum sulfate, this ratio is ca. 2.30, whereas
the theoretical value is 2.35. This weakly basic
aluminum sulfate has the advantage that it is less
hygroscopic and therefore hardly affects either
the metal parts of the apparatus during use or
paper sacks during transport. Also, free acid
damages cellulose fibers in the paper industry.
1.1.3. Uses
About two thirds of the total aluminum sulfate
production is used for treating water. About one
half of the total production goes into the paper
industry (paper sizing, pH adjustment, wastewa-
ter purification) [17, p. 246].
Paper Industry. Aluminum sulfate is used
for precipitating and fixing sizing agents, wet-
strength agents, and basic dyes; for improving
retention; for dispersing resin particles that stick
together and block sieves; as the starting material
of a high-quality slip for coating glossy paper
(satin white); and for the production of lake dyes
and wallpaper. For an overview of uses in news-
paper factories, see [18]; for a detailed discussion
on the importance of aluminum sulfate in paper
production, see [5]. Aluminum sulfate with more
than 0.2 % Fe2O3 gives paper a yellow tinge and
cannot be used for good-quality white paper.
Water Purification. Aluminum sulfate is
an important flocculating agent for purifying
Insoluble material, wt % Basicity*, %
– 1
0.04 0.1 – 1.0
0.04 0.1 – 1.0
0.03 0.1 – 1.0
< 0.03 0.8 – 1.5
ca. 0.03 1.0 – 1.8
Vol. 2
water [19]. The mechanism is as follows: Posi-
tively charged aluminum ions, which are hydrat-
ed or hydroxylated with water via numerous
intermediate stages, neutralize the negative
charge on the colloidal material in the water. As
a result of mutual adsorption, the material floc-
culates, sediments at various rates, and finally
settles as sludge after 15 – 150 min. To neutral-
ize the hydrogen atoms formed on hydrolysis of
aluminum sulfate, some carbonate hardness is
consumed:
Al2 ðSO4 Þ3 þ6 HCO 2
3 !2 AlðOHÞ3 þ6 CO2 þ3 SO4
For 50 mg/L of the 17 – 18 % Al2O3 grade
0.25 mmol/L of carbonate hardness (based on
alkaline-earth ions) is consumed. Generally, 5 –
50 g aluminum sulfate is sufficient to purify 1 m3
of water. An advantage of using aluminum
sulfate is the lack of postflocculation, provided
the correct amount is added. Disadvantages
are the formation of free carbon dioxide, the
increase of non-carbonate hardness, such as
calcium sulfate, and the pH remaining between
5 and 7. If no natural bicarbonate hardness is
present, an alkaline substance that also has a
dispersing effect, such as lime or sodium alumi-
nate, must be added. Aluminum sulfate, used
in combination with calcined leached clay, is
suitable for binding mercury ions, for example,
in sea water [20].
Other Uses. Aluminum sulfate with a very
low iron content (below 0.01 %) is used as a
mordant in dyeing; a higher iron content is
unacceptable because this leads to color changes.
Further uses are for pickling of seeds, deodoriz-
ing of mineral oils, tawing, and producing alu-
minum hydroxide gel employed, for example, as
a filler for synthetic rubber. Aluminum sulfate
has some importance also as a catalyst support.
Finally, it is the starting material for almost all
other aluminum compounds.
Production and Capacity Data. Alumi-
num sulfate production in the USA was
1 168 000 t in 1980 and 1 075 000 t in 1982
[21]; that in Japan was 757 000 t in 1980 [22].
The main U.S. producer of aluminum sulfate is
Allied Corp. The main Japanese producers are
Nikkei Kako Co. and Scintoma Aluminum
Smelting Co.
Aluminum Compounds, Inorganic 573
1.2. Alums
Historical Aspects. Alumen, from which
the word alum is derived, was known to the
ancient Greeks and Romans as an astringent and
also as a mordant in dyeing wool. Alum was
employed in processing skins, for embalming
animal and human corpses, and for fireproofing
wood. However, what was known at first as
alum was not a defined substance but referred
to both alum-containing minerals and mixtures of
alum with iron vitriol. PARACELSUS was the first to
distinguish true alum from iron vitriol. In the
years 1776 – 1798, CHAPTAL and VAUQUELIN es-
tablished that alum was a double salt of potassi-
um and aluminum sulfates and that the potassium
ions could be replaced by ammonium ions. The
raw material of the ancient alum industry was
alum stone (alunite) or alum shale. Alum stone
contains all components of the alum in the correct
ratios and is processed by roasting and leaching.
Roasting, aging for several years, and leaching of
alum shale gave an aluminum solution from
which the alum was precipitated with alkali. The
alum industry played an important role during the
whole of the Middle Ages.
The industrial production of the alums ceased
to have particular importance when it became
possible to produce aluminum sulfate economi-
cally in high purity, because only the aluminum
content is of practical importance. Most of the
alum production methods now have only limited,
partly only historical, interest. Clay and other
alkali-containing silicates, particularly bauxite,
were used as raw materials and were digested
using alkali or acid. Today, alums are produced
only from aluminum hydroxide, which is
obtained by the Bayer process from bauxite
(! Aluminum Oxide).
General Properties. Alums are crystalline
double salts of the general formula (cation 1)þ
(cation 2)3þ (anion2)2
12 H2O. The most
useful alums are those with trivalent aluminum
cations and sulfate anions, MþAl3þ(SO2 4 )2

12 H2O. The individual components of the alum
can be replaced, retaining both the regular crys-
talline form and the hydrate water. Alums with
the following trivalent metals are known: iron,
chromium, cobalt, manganese, titanium, vana-
dium, gallium, indium, scandium, rhodium, and
iridium. The monovalent component can be an
574 Aluminum Compounds, Inorganic
alkali metal, or it can be ammonium, alkylam-
monium, arylammonium, or thallium. The ex-
istence of a lithium alum is uncertain. Known
combinations include potassium–aluminum,
cesium–aluminum, potassium–chromium, and
hydroxyammonium–aluminum. A selenate al-
um also is known: KAl(SeO4)2
12 H2O.
All alums crystallize in strongly refracting
octahedra or cubes [1]. They have an astringent
taste and rot-proofing, protein-precipitating
properties.
In aqueous solution, alums show all the
chemical properties that their components show
separately. Physical properties, such as color,
electrical conductivity, and freezing-point
lowering, are the sum of the properties of the
components, provided the solutions are very
dilute. At higher concentrations, complexes,
such as [Al(SO4)2
(H2O)2], are formed. The
solubilities of the alums in water decrease from
sodium to cesium (see Table 3). On heating, the
alums lose their water of crystallization either
partially or completely. However, part of the
water is taken up again at normal temperature
and humidity.
1.2.1. Potassium Aluminum Sulfate
Potassium aluminum sulfate [7784-24-9], known
as potassium alum, KAl(SO4)2
12 H2O, r 1.75
g/cm3, Mr 474.4, and ammonium aluminum sul-
fate are the aluminum compounds known lon-
gest. Potassium alum occurs in nature as efflo-
rescence on alum shale and in volcanic areas on
trachyte and lava as feather alum.
Potassium alum crystallizes in large, color-
less, transparent octahedra, which melt at
92.5  C in their own water of crystallization.
The hardness of the crystals on the Mohs scale
is 2. The octahedra absorb long-wavelength IR
radiation almost completely, but are transparent
Table 3. Solubility of some aluminum alums as a function of temperature (grams of anhydrous salt per 100 g water)
t,  C 0 10 20 30 40
Sodium 56.2 60.5 61.5 66.7
Potassium 3.0 4.0 5.9 7.9 11.7
Ammonia 2.6 4.5 6.6 9.0 12.4
Rubidium 0.71 1.09 1.40
Cesium 0.2 0.3 0.4
Thallium 3.05 4.4 6.2 12.6
Vol. 2
to visible light. Certain substances (hydroxides,
carbonates, borates, carbamides, also metals and
organic dyes) promote the formation of basic
aluminum sulfate by binding free sulfuric acid
in the mother liquor. Under these conditions, the
cubic form is favored (cubic or Roman alum).
Potassium alum is stable in air of normal
humidity. Dehydration does not begin below
30  C, but at 65  C nine moles of water are lost.
Literature data on the dehydration are contradic-
tory. Investigations on thermal decomposition
are given in [23]. According to these results,
K2SO4, g-Al2O3, and 3 K2SO4
Al2(SO4)3 form
at 780  C, whereas K2SO4, a-Al2O3, and K2O

12 Al2O3 are produced at 1400  C. When heated
above its melting point, potassium alum dehy-
drates, forming calcined alum (alum ustum), KAl
(SO4)2 [10043-67-1]. At red heat, SO3 is released.
Potassium alum is soluble in dilute acid
but almost insoluble in anhydrous alcohol,
acetone, and methyl acetate. Because of the
marked increase in solubility in water with
temperature, potassium alum can be purified
more easily than other aluminum salts by recrys-
tallization and, in particular, can be freed from
iron sulfate. Mixed crystals form readily with
ammonium sulfate.
Basic potassium aluminum sulfate,
K[Al(OH)2]3(SO4)2
3/2 H2O, occurs in nature
as l€owigite. The compound is made synthetically
as a rather insoluble, amorphous powder by
heating aluminum sulfate, water, and an excess
of potassium sulfate or by heating potassium
alum with water in the ratio 1 : 4 to 200  C
[24]. Another basic potassium aluminum sulfate,
K[Al3(OH)6(SO4)2] [1302-91-6], containing less
water, is the alum stone (alunite) occurring in
nature.
Production. Aluminum hydroxide (wet hy-
drate; Al2O3 ca. 57 %, Fe2O3 0.016 – 0.023 %,
50 60 70 80 90 100
17 25 40 71 109 154
15.9 21.1 26.9 35.2 50.3 70.8
3.1 4.98 21.6
0.8 1.24 5.3 22.8
26.0
Vol. 2
H2O 42.5 %) and sulfuric acid (r 1.6 g/cm3;
Fe2O3 0.020 – 0.040 g/L) react in a stirred,
corrosion-resistant pressure boiler at 5 – 6 bar
to form aluminum sulfate as shown in Figure 1.
The aluminum sulfate melt is then led,
with release of pressure, into a copper container.
Here, a stoichiometric quantity of potassium
sulfate (as chloride-free as possible) is added.
The solution is heated to ca. 100  C for 2 – 3 h
and adjusted to 40 – 44  B
e with mother
liquor. After filtration from insoluble material,
the alum melt is left in crystallization boxes
for 10 days, after which the alum is removed
in blocks. The product obtained in this
way contains < 0.001 % Fe2O3, 0.001 –
0.004 % chloride, and < 0.01 % insoluble
material.
For the production of alum crystals, the alum
melt is brought into a stirred crystallization bath,
where it is cooled to ca. 40  C by air bubbles. The
pulp is then separated from the mother liquor by
centrifuging and washed. The mother liquor is
collected and returned to the copper container.
The potassium alum is dried at 50 – 60  C. The
salt, which forms lustrous crystals, is sieved and
packed in paper bags that are lined with
polyethylene.
A process for obtaining potassium alum from
alum-containing ores is given in [15], and the
production of basic potassium and sodium alums
from synthetic alum is described in [25].
Uses. As already mentioned, the industrial
importance of potassium alum has declined
considerably. However, it is still employed in
tawing skins, as a mordant in dyeing, and as
a coagulating agent for latex. Because of its
astringent and protein-precipitating properties,
potassium alum is used in the pharmaceutical
and cosmetics industries. The use of potassium
alum as a styptic pencil, because of its blood-
stanching property, is very widespread and
popular. The most important application today
is in the gypsum industry, which employs
potassium alum as hardening agent and
setting accelerator for the production of marble
cement and alabaster plaster. However, for
purifying water and sizing paper, potassium
alum has been replaced completely by aluminum
sulfate. In the paper industry, aluminum sulfate
is designated traditionally, although incorrectly,
as an alum.
Aluminum Compounds, Inorganic 575
1.2.2. Ammonium Aluminum Sulfate
Ammonium aluminum sulfate [7784-26-1], also
called ammonium alum, NH4Al(SO4)2
12 H2O,
Mr 453.33, r 1.64 g/cm3, mp 93.5  C, occurs in
nature as shermigite. Crystals doped with other
alums show birefringence. The solubility of am-
monium alum in water is similar to that of
potassium alum, with which it forms a continu-
ous series of mixed crystals. Ammonium alum is
slightly soluble in dilute acids and glycerol but
insoluble in absolute alcohol. In aqueous solu-
tion, ammonium alum is neutral.
Data on loss of water on heating are in dis-
agreement. GEL’PERIN and CHEBOTKEVICH [26]
have reported that water of crystallization is
released in three stages: first to give the hydrate
with 21 mol water, then to that with 3 mol water,
and finally to the anhydrous product, so that it is
in fact more correct to formulate ammonium
alum with 24 mol water. Above 193  C, decom-
position with the release of ammonia begins. On
glowing above 1000  C, sulfur trioxide is lost,
leaving an aluminum oxide residue.
Production. Ammonium alum is made
mainly by dissolving aluminum hydroxide in
sulfuric acid and adding ammonium sulfate but
sometimes by the reaction of ammonia gas with
aluminum sulfate and sulfuric acid. The proce-
dure is analogous to the potassium alum process.
To obtain a quality particularly low in iron oxide
or other metal oxides (< 0.0001 % Fe2O3; nor-
mal quality ca. 0.001 % Fe2O3), as is required for
production of synthetic gems, very pure starting
materials must be used. Ammonium alum occurs
as an intermediate in the ‘‘aloton’’ process, which
operates in a sulfuric acid medium. This process
had some importance prior to 1945 in Germany
and the United States for aluminum hydroxide
and aluminum oxide production (! Aluminum
Oxide).
Uses. In Europe, ammonium alum is not
used in large quantities. Applications include
those in dressing furs in tanning, in the produc-
tion of very fine aluminum oxide particles for
polishing metallographic surfaces, and, in some
countries outside Europe, as a disinfectant. In the
United States, ammonium alum is important as
an additive in baking powder; ca. 500 t/a are
produced for this purpose. More recently,
576 Aluminum Compounds, Inorganic
ammonium alum has gained considerable impor-
tance as starting material for the production of the
finely powdered, loose aluminum oxide of high
purity that is required for synthesizing corundum
gems, such as rubies and sapphires. This quality
of aluminum oxide is made by heating ammoni-
um alum (or ammonium aluminum selenate al-
um) to 1000  C.
1.2.3. Sodium Aluminum Sulfate
Sodium aluminum sulfate [7784-28-3], sodium
alum, NaAl(SO4)2
12 H2O, melts at 61  C in its
water of crystallization. In nature, it occurs as the
mineral mendozite. Again, the data on thermal
dehydration disagree. Sodium alum is insoluble
in absolute alcohol but is much more soluble in
water than all other alums. Alum powder (very
fine crystalline form) is not available commer-
cially. These two facts make it difficult to obtain
sodium alum free from iron. Because of this and
also because of its strong tendency to age, sodium
alum has never gained the same importance as
the other alums. In Europe, its use has been
abandoned. In the United States, however, sodi-
um alum is still utilized in relatively large quan-
tities (ca. 3000 t/a) in baking powder.
Production. In the United States, sodium
alum is produced by adding a clear solution of
sodium sulfate to aluminum sulfate. After dilu-
tion to 30  B
e and subsequent heating, a sludge
of potassium sulfate, sodium silicate, and caustic
soda is added to improve the purity of the prod-
uct. The mixture is pumped into a stirred vessel,
where it is mixed for several hours. During this
stage, the ratio of aluminum sulfate to sodium
sulfate is adjusted to the stoichiometric amount.
Afterwards, the melt is pumped into an evapora-
tor and concentrated to such an extent that it
solidifies to a hard cake on pouring into a cooling
tank. This sodium alum cake is then heated and
finally ground to the desired size (99 % through a
sieve of 100 mesh) [17, p. 250].
2. Aluminates
Only the aluminates of barium and sodium have
importance in industry. Aluminates occur also in
cement and in spinels.
Vol. 2
2.1. Sodium Aluminate
Sodium aluminate [1302-42-7] is an important
commercial inorganic chemical. It functions as
an effective source of aluminum hydroxide for
many industrial and technical applications. Com-
mercial grades of sodium aluminate are available
in solid and liquid forms. Pure sodium aluminate
(anhydrous) is a white crystalline solid having a
formula variously given as NaAlO2, Na2O

Al2O3, or Na2Al2O4. Commercial grades, how-
ever, always contain more than the stoichiomet-
ric amount of Na2O, the excess being on the order
of 1.05 to 1.50 times the formula requirement.
Hydrated forms of sodium aluminate are crystal-
lized from concentrated solutions.
Sodium aluminate has no defined melting
point; it softens above 1700  C when sodium
begins to evaporate slowly, leaving aluminum
oxide.
Production. The chief commercial process
for the manufacture of sodium aluminate is the
dissolution of aluminum hydroxides in sodium
hydroxide solution. Aluminum trihydroxide
(gibbsite) from the Bayer process (! Aluminum
Oxide) can be dissolved in 10 – 30 % aqueous
NaOH solution at a temperature near the boiling
point.
The use of more concentrated NaOH solutions
leads to a semisolid product. The process is
carried out in steam-heated vessels of nickel or
steel, and the aluminum hydroxide is boiled
with ca. 50 % aqueous sodium hydroxide until
a pulp forms. After this is poured into a tank and
cooled, a solid mass containing about 70 %
NaAlO2 is formed. After being crushed, this
product is dehydrated in a rotary oven heated
either directly or indirectly by burning hydrogen.
The resulting product contains ca. 90 % NaAlO2
and 1 % water, together with 1 % free NaOH.
The solubility of the salt produced in this way
depends strongly on how much excess sodium
hydroxide is used.
Alternatively, bauxite can be used directly as
the alumina source. Bauxites containing gibbsite
are extracted at 150  C and 5 bar, whereas
boehmite containing bauxite requires higher
temperatures (230  C) and pressures. The sodi-
um aluminate solution obtained from the diges-
tion process is separated from any impurities and
then concentrated to the commercial liquid grade
Vol. 2
by evaporation. The solid product is obtained by
drying the liquid.
The sinter method also has been used to
produce sodium aluminate. By sintering sodium
carbonate directly with Bayer aluminum trihydr-
oxide in rotary sintering kilns at 1000  C, an
essentially anhydrous product can be obtained.
When sintering bauxite, it is essential to leach the
sinter mass with water and separate the
impurities.
Uses. The major use of sodium aluminate is
for water treatment, including both potable and
industrial waters. Sodium aluminate is used as an
adjunct to water softening systems, as a coagu-
lant aid to improve flocculation, and for remov-
ing dissolved silica. Sodium aluminate dissolves
in water to give a solution that has a pH value of 8.
The aluminum hydroxide that precipitates from
this solution has excellent flocculation properties
and coagulates other impurities present in the
water. Depending on the impurities, the condi-
tions of precipitation can be improved by adding
aluminum sulfate [27].
In construction technology, sodium aluminate
is employed to accelerate the solidification of
concrete, mainly when working during frost,
under water, and in humid soil (see Table 4).
Compared to calcium chloride, which acts in a
similar manner, sodium aluminate has the advan-
tage of greater setting acceleration at low water-
to-cement ratios [28]. Because it does not attack
the reinforcing metals, it can be used for work
with steel-reinforced concrete. Too rapid setting
can cause cracks in the concrete, affecting the
final strength of the building. By adding sub-
stances such as oxoacids [29], sugar, naphthene
[30], K2CO3, or Na2SO4 [31] the final strength
increases without affecting the setting rate sig-
nificantly. Sodium aluminate increases the resis-
tance of mortar to water, alkali, and acid. For the
production of expanded concrete, sodium alumi-
Table 4. Acceleration of setting by sodium aluminate in a mixture of 6
parts sand, 2 parts concrete, and 1 part water
% NaAlO2 in concrete Setting started Setting completed
0 4 h 30 min 6h
1 30 min 1 h 40 min
1.5 15 min 30 min
2 10 min 15 min
10 instantly
Aluminum Compounds, Inorganic 577
nate serves to activate nitrogen-releasing sub-
stances [32]. To stabilize foam formation in the
production of light refractory bricks, up to 5 %
(relative to the total dry mass) sodium aluminate
is added.
Increasingly, sodium aluminate is being used
for the production of synthetic zeolites, used as
catalyst supports or as catalysts [33–36] and as
adsorbents. Sodium aluminate is one of the prin-
cipal sources of alumina of the preparation of
alumina adsorbents and catalysts.
In the paper industry, sodium aluminate in-
creases the opacity [37], retention of fibers and
filling materials [38], and the paper strength [39].
Also, it stabilizes the pH value of the water
circulation [40] and increases the dispersion
stability of titanium dioxide [41].
Another application of sodium aluminate is as
a pickle to protect metallic surfaces (copper [42],
aluminum [43], among others). This effect is
based on the formation of a thin, very firmly
adhering layer of aluminum hydroxide or, after
heat treatment, of aluminum oxide on the surface,
which does not affect the metallic luster. In the
enamel industry, sodium aluminate is added to
enamel mixtures to achieve low-melting covers
[44].
Further applications of sodium aluminate are
in lithography for the production of printing inks
[45] and print forms [46], in the detergent and
varnish industries, in the production of water-
insoluble floor waxes [47], as a dispersion agent
for production of high-purity asbestos [48], as an
additive to drilling fluids [49], and in the textile
industry as a mordant in dyeing and in printing
cloth. Many other uses of sodium aluminate have
been reported. These include inhibition of glass
etching by alkaline solutions; protection of steel
surface during galvanizing; improving dyeing,
antipiling, and antistatic properties of polyester
synthetic fibers; as an additive to foundry sand
molds and cores; and as a binder in the ceramics
industry.
2.2. Barium Aluminates
The industrially important barium aluminates are
BaO
6 Al2O3 [12254-17-0], mp 1915  C; BaO

Al2O3 [12004-04-5], mp 1815  C; and 3 BaO

Al2O3 [12004-05-6], mp 1425  C [50]. The first
two crystallize hexagonally.
578 Aluminum Compounds, Inorganic
Barium aluminates are produced by melting
bauxite with coal and barite. Leaching the melt
gives a solution of barium aluminate, from which
the salt is obtained by evaporation. Very pure
barium aluminates can be produced by sintering
mixtures of aluminum oxide with barium car-
bonate. All barium aluminates, including such
hydrated compounds as BaO
Al2O3
4 H2O,
2 BaO
Al2O3
5 H2O, BaO
Al2O3
7 H2O,
and 7 BaO
6 Al2O3
36 H2O, hydrolyze in
water, forming hydrargillite (gibbsite), Al(OH)3,
and relatively soluble barium hydroxide.
Barium aluminate is used for purifying water
because the Ba2þ ion precipitates both the sul-
fates and the carbonates, whereas the aluminate
ions form insoluble calcium aluminate. A further
use of barium aluminates is as a special cement,
for example, as binding agent for the production
of high-temperature refractories, and in the pro-
duction of radiation shields [51].
3. Aluminum Alkoxides
Aluminum alkoxides (alcoholates) are solid or
liquid compounds of covalent character. They are
readily soluble in hydrocarbons, but sparingly sol-
uble in alcohols. Hydrolysis with water occurs
readily, giving aluminum hydroxide and the cor-
responding alcohol. For a general review of alumi-
num alkoxides, see [52]. Industrially, only the
isopropoxide (isopropylate) and sec-butoxide
(sec-butylate) are important. These compounds are
used to adjust the viscosity of varnishes, to impreg-
nate textiles, as intermediates in the production of
pharmaceuticals, and as antitranspirants in cos-
metics. In the industrial production of ketones and
aldehydes, aluminum alkoxides are employed as
reducing agents (Meerwein-Ponndorf reaction).
Aluminum isopropoxide [555-31-7], Al
(OCH(CH3)2)3, is a white solid, Mr 204.25, mp
118  C, bp 125 – 130  C at 533 Pa, d420 1:0346,
flash point 26  C. It is usually produced by direct
reaction of aluminum and isopropyl alcohol in
the presence of mercury(II) chloride catalyst. In a
later version of the process [53], the alcohol
was heated under reflux in a column filled with
aluminum chips; no catalyst was required and
nearly quantitative conversion was obtained. The
alkoxide can be purified by distillation. In an
alternative production method, excess isopropyl
Vol. 2
alcohol is added to a solution of aluminum
chloride in benzene; the hydrogen chloride
formed is removed by introducing dry ammonia
into the reactor and filtering off the ammonium
chloride that precipitates.
Aluminum sec-butoxide [2269-22-9],
Al(OC4H9)3, is a colorless liquid, Mr 246.3, bp
180  C at 533 Pa, d420 0:9671, flash point 26  C,
and is produced in a manner similar to aluminum
isopropoxide.
4. Aluminum Chloride
4.1. Anhydrous Aluminum Chloride
OERSTEDT first prepared anhydrous aluminum
chloride [7446-70-0] in 1825 by the reaction of
chlorine gas with a mixture of alumina and carbon.
This compound has acquired great significance in
organic chemistry as a catalyst, particularly for
Friedel-Crafts syntheses and allied reactions for
the production of alkylated aromatics, dyestuffs,
pharmaceuticals, and perfumery chemicals. For
general literature, see [1] and [54].
4.1.1. Properties
Physical Properties. In the solid and gas
phases at temperatures up to 400  C, aluminum
chloride is present as the dimer, Al2Cl6. Dissocia-
tionofthedimerprogresseswithrisingtemperature
and is quantitative above 800  C. Solid aluminum
chloride crystallizes to form a monoclinic layer
lattice. Pure aluminum chloride is white, but the
commercial product usually has a yellowish or
grayish tinge because of small amounts of iron
chloride or aluminum impurities. Physical proper-
ties of anhydrous aluminum chloride [55]:
Mr 133.34
r at 25  C 2.44 g/cm3
Sublimation temperature 181.2  C
at 101.3 kPa
Triple point, at 233 kPa 192.5  C
Heat of formation at 25  C –705.63  0.84 kJ/mol
Heat of sublimation of dimer 115.73  2.30 kJ/mol
at 25  C
Heat of fusion 35.35  0.84 kJ/mol
Heat of solution at 20  C –325.1 kJ/mol
Vol. 2
Chemical Properties. Anhydrous alumi-
num chloride reacts extremely violently with
water, evolving hydrogen chloride. The hexahy-
drate [7784-13-6], AlCl3
6 H2O, Mr 241.44, is
formed in this reaction. In aqueous solution,
aluminum chloride is partially hydrolyzed to
hydrochloric acid and aluminum oxychloride,
AlClO [13596-11-7]. For this reason, anhydrous
aluminum chloride cannot be obtained by con-
centrating the solution and calcining the hydrate.
When aluminum chloride is heated with g-alu-
mina, aluminum oxychloride, AlClO, forms, but
this reaction goes in the reverse direction at
temperatures above 700  C:
AlCl3 þAl2 O3
3 AlClO clusion of moisture), and classified by sieving.
If aluminum chloride vapor is passed at
1000  C under reduced pressure over molten
aluminum, volatile aluminum monochloride
[13595-81-8], AlCl, is formed, but this decom-
poses immediately into the elements in cooler
zones of the reactor. This method has been
adopted for purifying aluminum.
Reaction between aluminum chloride and
other metal halides, such as CaCl2, CrCl3, and
FeCl3, gives mixed halides. Eutectic melts
with other metal chlorides are of industrial
significance, for example, that with sodium
chloride is used as a solvent in chlorination
reactions.
Anhydrous aluminum chloride dissolves
readily in polar organic solvents. As a Lewis
acid it forms addition compounds with numerous
electron donors, such as hydrogen chloride, hy-
drogen sulfide, sulfur dioxide, sulfur tetrachlo-
ride, phosphorus trichloride, ethers, esters,
amines, and alcohols.
4.1.2. Production
The starting materials are either aluminum or
pure aluminum oxide. Bauxite now has no eco-
nomic significance as a raw material because of
the iron chloride always present in the product.
Chlorination of Aluminum [56]. Today,
most anhydrous aluminum chloride is made by
chlorinating aluminum.
Chlorine is passed through molten aluminum
in ceramic-lined, tube-shaped reactors. The re-
action is highly exothermic:
Aluminum Compounds, Inorganic 579

2 AlðsÞþ3 Cl2 ðgÞ!Al2 Cl6 ðsÞ DH ¼ 1411 kJ=mol
The temperature in the reactor is maintained at
670 – 850  C by controlling the admission rates
of chlorine and aluminum and by cooling the
reactor walls with water. The aluminum usually
is replenished in the form of lumps. The difficulty
of controlling the large heat of reaction can be
overcome also by dividing the process into a
number of small units.
The aluminum chloride vapor leaving the
reactors is passed through ceramic-lined tubes
into large, air-cooled iron chambers. Solid alu-
minum chloride is withdrawn from the condenser
walls at regular intervals, ground (insuring ex-
Chlorine in the off-gas is removed by conven-
tional methods, such as absorption in caustic soda
solution.
Chlorination of Pure Aluminum Oxide.
Chlorination of alumina is advantageous over the
formerly widely used bauxite process (less reac-
tor corrosion and higher-purity product), and at
the same time it avoids the high raw material
costs involved in metal chlorination [57].
Carbon monoxide and chlorine are partially
converted to phosgene over an activated char-
coal catalyst. The gaseous reaction mixture
enters a brick-lined, fluidized-bed reactor,
where it reacts with finely divided g-alumina
to yield aluminum chloride. The reaction is
exothermic enough (ca. 300 kJ/mol, based on
AlCl3) to maintain the temperature at 500 –
600  C without external heat. Consequently,
the process permits large units, and the low
reaction temperature insures that the brick lin-
ing has a long life.
The aluminum chloride vapor is filtered
through a bed of coarse pumice chips, condensed,
and further processed as described above. The
off-gas contains chlorine, phosgene, and large
amounts of carbon dioxide. The chlorine is re-
moved by scrubbing, and the phosgene is hydro-
lyzed with water. Extremely pure aluminum
chloride is obtained by resublimation from mol-
ten sodium aluminum chloride.
4.1.3. Quality Specifications and Analysis
Anhydrous aluminum chloride is ground and
marketed as powder or granules. Aluminum is
580 Aluminum Compounds, Inorganic
usually determined by atomic spectrometry, the
chloride by argentometry. The assay is 98 –
99 % AlCl3. The main impurity is iron
(0.05 wt % max. or 0.01 wt % for resublimed
product). Sampling and analysis of anhydrous
aluminum chloride must be carried out in an
atmosphere of dry air or nitrogen.
4.1.4. Handling, Storage, and
Transportation
Because of its corrosive and irritant action, an-
hydrous aluminum chloride is classified as a
dangerous substance. National and international
regulations must be observed, such as 67/548/
EEC, the key European Economic Community
directive dealing with the classification, packag-
ing, and labeling of dangerous substances.
Handling. Goggles, gloves, and protective
clothing must be worn when handling aluminum
chloride. A fume cupboard or a respirator with
filter type B/St against acid gases should be used.
Because hydrogen chloride is evolved when
aluminum chloride is exposed to water, any spills
must be taken up dry, and only small, residual
amounts can be washed away with plenty of
water. Sodium bicarbonate or slaked lime should
be used for neutralization.
Storage and Transportation. Aluminum
chloride is dispatched in vented steel drums or
in tank trucks or rail tankcars that can be emptied
pneumatically with dry air or nitrogen (dew point
below  40  C). Because the product tends to
cake, it should not be stored for more than six
months. International marine transportation is
governed by the IMDG code, class 8, UN
no. 1726. RID, ADR, ADNR: Class 8, no. 11b,
Rn 801, 2801, 6801, respectively. EEC: Yellow
Book 78/79, EG no. 013003007. UK: Blue
Book, Corrosives & IMDG code E 8031. USA:
DOT regulations, corrosive solid, CFR 49,
172.101.
4.1.5. Uses
Anhydrous aluminum chloride is an important
Friedel-Crafts catalyst in the chemical and pet-
rochemical industries [58, 59]. A principal ap-
Vol. 2
plication is the alkylation of benzene by alkyl
halides to form alkylbenzenes that are consumed
in the production of synthetic detergents, such as
alkylbenzenesulfonates. Aluminum chloride al-
so catalyzes the liquid-phase ethylation of ben-
zene with ethylene to yield ethylbenzene, most of
which is used in the production of styrene.
Ethyl chloride is produced mainly by the
reaction of hydrochloric acid and ethylene in the
presence of aluminum chloride; the consumption
has significantly decreased because of the declin-
ing demand for tetraethyl lead as an antiknock
additive.
In the dyestuffs industry, aluminum chloride
is widely used as catalyst in the production of
anthraquinone and its derivatives and of pig-
ments, such as phthalocyanine green. A further
application of aluminum chloride is as a finish for
titanium dioxide pigments, which are in this way
protected from oxidation by an oxide layer.
Until 1960, aluminum chloride was used ex-
tensively in petroleum refining for cracking and
isomerization, but it has now been replaced by
zeolite catalysts. It is still employed in reforming
hydrocarbons, as a polymerization catalyst in the
production of hydrocarbon resins, and for the
production of butyl rubber.
It is a catalyst also in the production of com-
pounds, such as aromatic aldehydes, ketones, and
2-phenyl-ethanol, used in fragrances. Other ap-
plications for anhydrous aluminum chloride in-
clude the production of aluminum borohydride,
lithium aluminum hydride, as well as compounds
of phosphorus and sulfur.
Most of these reactions with aluminum chlo-
ride produce a solution that is often used as a
flocculating agent in the treatment of waste
water.
Aluminum chloride also is an intermediate in
the production of aluminum by the Alcoa smelt-
ing process [60] (! Aluminum).
Data on the consumption of anhydrous alumi-
num chloride in the USA are given in Table 5.
4.2. Aluminum Chloride Hexahydrate
Properties. The white hydrate AlCl3

6 H2O [7784-13-6], Mr 241.43, crystallizes hex-
agonally and dissolves exothermally in water
(133 g hexahydrate per 100 g water at 20  C)
[62]. The solubility increases only slightly with
Vol. 2
Table 5. U.S. anhydrous aluminum chloride consumption in 1993 (not
including the amounts consumed in the production of aluminum) [61]
Alkylate detergents 2200 t
Ethylbenzene 4000 t
Hydrocarbon resins 3900 t
Pharmaceuticals 4000 t
Titanium dioxide 2200 t
Miscellaneous 4900 t
Total 21200 t
temperature. The aqueous solutions are strongly
acidic because the salt hydrolyzes. Hydrogen
chloride is evolved on heating concentrated so-
lutions. The structure of aqueous solutions of
AlCl3
6 H2O is discussed in [63].
Production and Uses. Aqueous solutions of
AlCl3
6 H2O can be obtained by dissolving
aluminum hydroxide in hydrochloric acid: the
hexahydrate crystallizes when hydrogen chlo-
ride passes into cold (about 20  C) saturated
solution. In this way, impurities, particularly iron
(III) chloride, can be removed [62]. Aluminum
chloride hexahydrate has only minor importance
as such; for example, it is used for hardening
photographic layers. However, it is of industrial
importance as an intermediate in the production
of aluminum oxide [64, 65].
4.3. Basic Aluminum Chlorides
Properties. Basic aluminum chlorides
[1327-41-9], aluminum hydroxychlorides, alu-
minum chloride hydroxides, poly(aluminum hy-
droxychlorides), have the general formula
Al2(OH)6nCln
x H2O. The individual com-
pounds are best defined either by the molar ratio
of aluminum to chloride (2/n) or by their basicity,
defined as (1 – n/6)
100 %. Below a minimum
water content, which depends on n, the com-
pounds are unstable; they decompose to alumi-
num hydroxide and aluminum oxide on heating
to above 80  C, releasing water and hydrogen
chloride. All basic aluminum chlorides with
n ¼ 1 – 5 can be isolated, and all are white, in
some cases crystalline substances, partially sol-
uble in the lower alcohols [66, 67], but readily
soluble in water. For example, 170 g of the
compound Al2(OH)5Cl
2.5 H2O dissolves in
100 g water at 20  C. However, the viscosity of
the solution prevents further amounts from dis-
Aluminum Compounds, Inorganic 581
Figure 2. Electrical conductivity of freshly prepared basic
aluminum chloride solutions: *) from Locron L (ca. 50 %
aqueous solution of Al2(OH)5Cl
2.5 H2O) and hydrochloric
acid at constant aluminum oxide concentration (11.5 %) and
20  C; ~) prepared directly from AlCl3
6 H2O
solving. The electrical conductivities of the
aqueous solutions, shown in Figure 2, are char-
acteristic of the basic aluminum chlorides.
Aqueous solutions of basic aluminum chlor-
ides are acidic because the compounds hydrolyze
(see Table 6). The stability of the solutions de-
pends on the basicity: compounds with alumi-
num to chloride molar ratios of ca. 0.5 : 1 to
about 1.6 : 1, corresponding to basicities of ca.
30 – 75 %, decompose to give insoluble basic
aluminum chloride at a rate that depends on the
temperature and concentration of the solution
[68]. On the other hand, compounds of basicity
greater than 75 % are very stable in aqueous
solution. For example, compounds with the ap-
proximate composition Al2(OH)5Cl
2 –
3 H2O [12042-91-0] are so stable at concentra-
tions > 50 % that no decomposition occurs, even
on boiling for days.
Table 6. pH values of aqueous solutions of Al2(OH)5Cl
2.5 H2O at
20  C (mass fractions, w, in %)
w pH
60 3.4
30 4.0
15 4.2
10 4.3
5 4.4
3 4.4
582 Aluminum Compounds, Inorganic
In contrast to the aluminum chlorides of low
basicity (below 65 %), the compounds of high
basicity (above 65 %) do not crystallize from
their aqueous solutions, but form glassy masses.
When solutions in the basicity range 30 – 65 %
are evaporated, the compound Al2(OH)3.7Cl2.3

6.05 H2O (basicity 62 %) always crystallizes
[69]. On addition of alkali to basic aluminum
chlorides, aluminum hydroxide precipitates. Hy-
drochloric acid converts all basic aluminum
chlorides to the hexahydrate:
Al2 ðOHÞ5 Clþ5 HClþ7 H2 O!2 AlCl3
6 H2 O
Chemical Structure. Basic aluminum
chlorides have been known for a long time
[1, p. 205], but only recently have investigations
given significant insight into their chemical
structures [70–73]. Basic aluminum chlorides
are mixtures of complex compounds of various
degrees of polymerization. Spectroscopic and
kinetic investigations of the basic aluminum
chlorides and of their solutions [70–73] lead
to the conclusion that the complex ion
[Al13O4(OH)24(H2O)12]7þ is present and is in
equilibrium with its polymeric forms. Variations
observed in the properties of these aqueous solu-
tions such as viscosity and pH are caused by
polymerization and depolymerization [74].
Analysis. Basic aluminum chlorides are so
stable that the aluminum content can be deter-
mined only after decomposition of the complex
ion [75, 76]. The usual procedure is to mix the
solution containing aluminum with 60 % sulfuric
acid and 0.1 M disodium ethylenediaminetetra-
acetate, followed by ca. 20 % sodium hydroxide.
The pH is adjusted to 4.7 – 4.9 at 60 – 70  C.
After the solution is cooled to about 25  C and
buffer solution (acetic acid, ammonium acetate),
acetone, and indicator (dithizone in ethanol) are
added, the solution is back-titrated with 0.1 M
zinc sulfate. One milliliter of 0.1 M disodium
ethylenediaminetetraacetate is equivalent to
2.698 mg of aluminum.
Production. Basic aluminum chlorides are
made by dissolving either aluminum hydroxide
or metallic aluminum in hydrochloric acid. Aged
aluminum hydroxide leads only to compounds of
basicity up to 65 % [68]. To obtain aluminum
chlorides of high basicity, freshly precipitated
Vol. 2
aluminum hydroxide [77] must be used. Howev-
er, the preferred method is to dissolve aluminum
in hydrochloric acid either thermally or electro-
chemically:
2 AlþHClþ5 H2 O!Al2 ðOHÞ5 Clþ3 H2
This method is exemplified by the following
process [78]:
Aluminum electrodes are set up at distances of
40 mm in a corrosion-resistant electrolysis cell.
Hydrochloric acid (r 1.04 g/cm3) is poured into
the cell at a rate such that the reaction tempera-
ture remains at ca. 80  C. After all the hydro-
chloric acid has been added, the voltage between
the first and last electrodes is set so that an
average voltage of 0.6 V per electrode pair is
obtained at a current density of ca. 170 A/m2.
The formation of explosive gas mixtures must be
avoided throughout the reaction by diluting the
hydrogen with air or nitrogen to below the ex-
plosion limit. After about 70 h, the density of the
electrolyte increases to about 1.2 – 1.3 g/cm3,
and the pH value to about 3.5. At the same time
the cell voltage falls. The electrolyte then con-
sists of a solution containing aluminum and
chloride in the molar ratio 2 : 1, corresponding
to a basicity of 83 %. The corresponding bro-
mides as well as iodides are obtained by the same
method. The solid halides are obtained from the
solutions by careful evaporation or by spray
drying [79]. Recently another method may be
of interest: Controlled thermic decomposition of
AlCl3  6 H2O [86].
Uses and Quality. The most important ba-
sic aluminum chloride with regard to consumed
quantities are the polyaluminum chlorides
(PAC) with basicities in the range of 35 –
60 %. PAC is widely used as a flocculating
agent for purifying water. In water treatment
PAC can be used for purifying surface water,
sewage, and wastewater from industry and mu-
nicipalities and for water treatment in swim-
ming pools. A second important application for
PAC is as fixing sizing agent in the paper
industry. Because of the change from acidic to
neutral or alkaline sizing, large quantities of
aluminum sulfate had to be substituted by PAC.
Various qualities are available with aluminum
contents between 7.5 and 18.0 %, calculated as
aluminum oxide.
Vol. 2
Another important basic aluminium chloride
has the composition Al2(OH)5Cl
2 – 3 H2O
and is known in the literature as aluminum
chlorohydrate. Very stringent purity specifica-
tions apply to this substance. The maximum
levels permitted are Fe 100 ppm, SO4 500 ppm,
Pb 20 ppm, As 3 ppm. These are required for
one of its major applications, namely, that in the
cosmetics industry as the effective component
of antiperspirants [80, 81]; trade names
are Chlorhydrol (Reheis, USA) and Locron
(Clariant). Other important areas of application
for this aluminum chloride are in the production
of catalysts and highly temperature-resistant
fibers based on Al2O3, as a hydrophobic agent
for impregnation of cotton textiles, for tanning
leather, as a retention agent in paper
production, as a binding agent for fire-resistant
ceramic products as a hardening agent for
rapid fixing baths in the photographic industry
and as a flucculant for purifying swimming-
pool water.
5. Toxicology
Aluminum sulfate is classified as nontoxic; an
LD50 value of 6207 mg/kg ( mouse, oral) is
reported [82]. Alum solutions are known for their
astringent (tissue-contracting) effects. A TLV of
2 mg/m3 was established for water-soluble alu-
minum salts [83].
Anhydrous aluminum chloride has a corrosive
and irritant effect on the skin, respiratory tract,
and eyes. The toxic effect is caused by the
evolution of hydrochloric acid when the
product is exposed to moist air. The resulting
respiratory difficulties vary from mild irritation
to coughing. The MAK value (1995) and TLV
(1983) for hydrochloric acid are both 7 mg/m3
[83, 84].
The extensive use of the basic aluminum
chloride Al2(OH)5Cl
2 – 3 H2O in the cosmet-
ic industry worldwide over more than 30 years
has shown that this compound is not irritating
to the skin in the concentrations used commer-
cially. Although intermittent application of
150 mg Al2(OH)5Cl
2 – 3 H2O over a
period of 3 days was found to cause mild skin
irritation in humans, a dose of only 7.5 mg
of AlCl3
6 H2O caused the same degree of
irritation [85].
Aluminum Compounds, Inorganic 583
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Further Reading
A. Bakac: Physical Organic Chemistry, Wiley, Hoboken N.J.
2010.
D. B. Mitzi (ed.): Solution Processing of Inorganic Materials,
Wiley, Hoboken, N.J 2009.
H. Stechemesser (ed.): Coagulation and Flocculation, 2nd
ed., Taylor & Francis, Boca Raton 2005.
G. E. Totten (ed.): Handbook of Aluminum, Volume 1:
Physical Metallurgy and Processes, Dekker, New York
2003.
G. E. Totten (ed.): Handbook of Aluminum, Volume 2: Alloy
Production and Materials Manufacturing, Dekker,
New York 2003.