Aluminum Compounds, Inorganic

Aluminum Compounds, Inorganic

Otto Helmboldt, Giulini Chemie GmbH, Ludwigshafen, Germany (Chap. 1 and 2)
L. Keith Hudson, Aluminum Company of America, Alcoa Center, Pennsylvania, USA (Chap. 2.1)
Chanakya Misra, Aluminum Company of America, Alcoa Center, Pennsylvania, USA (Chap. 2.1)
Karl Wefers, Aluminum Company of America, Alcoa Center, Pennsylvania, USA (Chap. 2.1)
Wolfgang Heck, BASF Aktiengesellschaft, Ludwigshafen, Germany (Chap. 3)
Hans Stark, BASF Aktiengesellschaft, Ludwigshafen, Germany (Chap. 4.1 and 5)
Max Danner, Hoechst Aktiengesellschaft, Werk Gersthofen, Augsburg, Germany (Chap. 4.2, 4.3 and 5)

Norbert Rosch,
Clariant Produkte (Deutschland) GmbH, Gersthofen, Germany
Related Articles Aluminum Oxide is a separate keyword. Aluminum uoride and cryolite Fluorine Compounds, Organic
1.
1.1.
1.1.1.
1.1.2.
1.1.3.
1.2.
1.2.1.
1.2.2.
1.2.3.
2.
2.1.
2.2.

Aluminum Sulfate and Alums

Aluminum Sulfate . . . . . . .
Properties . . . . . . . . . . . . . .
Production . . . . . . . . . . . . .
Uses . . . . . . . . . . . . . . . . .
Alums . . . . . . . . . . . . . . . .
Potassium Aluminum Sulfate .
Ammonium Aluminum Sulfate
Sodium Aluminum Sulfate . . .
Aluminates . . . . . . . . . . . .
Sodium Aluminate . . . . . . .
Barium Aluminates . . . . . . .

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1. Aluminum Sulfate and Alums

1.1. Aluminum Sulfate
Aluminum sulfate is the second most important industrial compound of aluminum, after aluminum oxide. Aluminum sulfate was rst 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 anhydrous alcohol but readily soluble in water; aqueous solutions are acidic. Literature data on solubility and the structure of the precipitate in water
differ markedly and should be used with caution
(see Table 1). Previously, Al2 (SO4 )3 18 H2 O
c 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a01 527.pub2

3.
4.
4.1.
4.1.1.
4.1.2.
4.1.3.
4.1.4.
4.1.5.
4.2.
4.3.
5.
6.

Aluminum Alkoxides . . . . . . . . . .
Aluminum Chloride . . . . . . . . . .
Anhydrous Aluminum Chloride . .
Properties . . . . . . . . . . . . . . . . . .
Production . . . . . . . . . . . . . . . . .
Quality Specications and Analysis .
Handling, Storage, and Transportation
Uses . . . . . . . . . . . . . . . . . . . . .
Aluminum Chloride Hexahydrate .
Basic Aluminum Chlorides . . . . . .
Toxicology . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . .

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10
10
10
11
11
12
12
13
13
15
15

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,
particularly, poor crystal formation make denitive characterization difcult [5]. The common
form of aluminum sulfate, generally considered
to be Al2 (SO4 )3 18 H2 O [7784-31-8], occurs
in nature as alunogen (hair salt) and can be
crystallized from hydrochloric acid solution as
microscopically 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 prepared readily and in high purity [1]. Other
well-dened 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 of the neutral salt, are described
in the literature [7]. The existence of aluminum

Aluminum Compounds, Inorganic

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 H2 O and Al2 (SO4 )3 Al(OH)3
H2 O systems [8, 9].
In industrial practice, the hydrate water content is unimportant because crystalline aluminum sulfate is a ground, microcrystalline
solid with variable water content, which is obtained from a melt. The desired Al2 O3 content is adjusted within certain limits by heating.
At a temperature above 340 C, anhydrous aluminum sulfate [10043-01-3] is formed, a white
powder,
2.71 g/cm3 , that decomposes above
770 C to aluminum oxide [9].
1.1.2. Production
In Germany and most European countries, aluminum 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 %, Fe2 O3 ca. 1 %) is still
important in some countries.
Giulini Process [10]. The Giulini method
for producing various grades of aluminum sulfate, containing between 8 and 23 % Al2 O3 , is
shown schematically in Figure 1.
A pressure-resistant, stirred vessel (a) is lled
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 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 insoluble basic aluminum sulfate and strongly acidic sulfate melt. An auto-

clave 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 ash evaporation (b). From
the evaporator, the melt is sucked into a wellisolated 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 conveyor belt (e), and crystallizes there in ca. 30
min. Because of the high heat of crystallization,
the material has a temperature of ca. 90 C and
cannot be broken to ne 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 lled (j) into paper or
jute sacks or transported loose in silo cars. Aluminum sulfate with 17.2 % Al2 O3 produced in
this way contains only 0.01 % insoluble material; therefore, digestion of the aluminum hydroxide is almost complete. For transportation
as a solution the Al2 O3 content is adjusted to ca.
8 % to avoid crystallization during transport.
Production from Bauxite. Finely ground
bauxite (for example, 60 % Al2 O3 , 1.5 % Fe2 O3 ,
1.6 % TiO2 , 3.0 % SiO2 , 32 % H2 O) also can
be used as starting material. In this case, 3 mol
H2 SO4 are charged onto 1 mol Al2 O3 . The
Fe2 O3 component in bauxite is disregarded because the Al2 O3 is only 97 98 % digested and
therefore sufcient sulfuric acid is available
for production of aluminum sulfate containing
17.5 % Al2 O3 . The aluminum sulfate obtained
by digestion of bauxite contains ca. 0.5 % Fe2 O3
and ca. 2.2 % insoluble residue.
Production from Less Pure Starting Materials. Acid digestion of predominately siliconrich 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 hexacyanoferrate (II) as Berlin blue (iron hexacyanoferrate (II)), with calcium sulde as iron
sulde, or by hydrolysis as basic iron sulfate.
For details, see [11]. The clear solution is de-

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
31.3
31.2
27.5
23.9

10
33.5
33.5
27.6
25.0

20
36.15
36.4
26.9

30
40.36
40.4
28.0

40
45.73
46.1
28.8
31.5

50
52.13
52.2
29.9

60
59.10
59.2
31.0
36.4

70
66.23
66.1
32.8

80
73.14
73.0
36.6
41.7

90
80.83
80.0
38.74

100
89.11
89.0
46.85
47.0

Reference
[1]
[2]
[3]
[4]

Figure 1. Production of aluminum sulfate by the Giulini process [10]

canted and sold as a liquid or concentrated to

61.5 Be, allowed to solidify, and milled. The nal product, which contains ca. 0.5 % Fe2 O3 and
0.1 % insoluble material, is the technical grade.
In addition, there is an iron-free grade having an
Fe2 O3 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 % Al2 O3 , 53

56 % SiO2 , 2 4 % Fe2 O3 ) with sulfuric acid.
The greater part of the impurities is removed
and crystals are separated from the solution by
stirring. The formation of colloids is avoided by
using vacuum apparatus. Pure, large crystals of
Al2 (SO4 )3 18 H2 O (15.3 % Al2 O3 ) can be separated easily from the impure mother liquor by

Aluminum Compounds, Inorganic

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 highquality 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-containing 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 ltration and removal of the sulfur dioxide in vacuo to give a pH of 4.5 5.0,
Al(OH)SO3 and SiO2 n H2 O precipitate. The
precipitate is ltered and treated with sulfuric
acid, whereby aluminum sulfate dissolves. [16].
Commercial Grades. Whereas Al2 (SO4 )3
18 H2 O theoretically contains 15.3 % Al2 O3 ,
commercial grades of aluminum sulfate contain 14 15 %, 15 16 %, 17 18 %, 18 %,
or 22 23 % Al2 O3 (Table 2). Generally, the
aluminum sulfate containing 17 18 % Al2 O3
(water-soluble aluminum content, calculated as
Al2 O3 ) is used most frequently. The calculated
hydrate water content of this aluminum sulfate is
13 mol. The commercial grade containing 17
18 % Al2 O3 is delivered also with various special qualities, such as low arsenic or low iron
content.
The basicity of the product is dened as the
excess in Al2 O3 over the stoichiometric SO3 :
Al2 O3 ratio. The 17 18 % Al2 O3 grade has a
basicity of 0.1 1 %, i.e., the Al2 O3 content exceeds the stoichiometric amount by 0.1 1 %.
Occasionally, the term basicity is dened as
the ratio % SO3 to % Al2 O3 . 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 bers 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, wastewater purication) [17, p. 246].
Paper Industry. Aluminum sulfate is used
for precipitating and xing sizing agents, wetstrength 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
newspaper 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 % Fe2 O3 gives paper a yellow tinge and cannot be used for good-quality
white paper.
Water Purication. Aluminum sulfate is an
important occulating agent for purifying water
[19]. The mechanism is as follows: Positively
charged aluminum ions, which are hydrated 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 occulates,
sediments at various rates, and nally settles as
sludge after 15 150 min. To neutralize the hydrogen atoms formed on hydrolysis of aluminum
sulfate, some carbonate hardness is consumed:
2
Al2 (SO4 )3 +6 HCO
3 2 Al (OH)3 +6 CO2 +3 SO4

For 50 mg/L of the 17 18 % Al2 O3 grade

0.25 mmol/L of carbonate hardness (based on
alkaline-earth ions) is consumed. Generally, 5
50 g aluminum sulfate is sufcient to purify 1
m3 of water. An advantage of using aluminum
sulfate is the lack of postocculation, 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

Aluminum Compounds, Inorganic

Table 2. Commercial grades of aluminum sulfate

Grade
8 % (solution)
14 15 %
15 16 %
17 18 %
18 %
22 23 %

Al2 O3 , wt %
8
14 15
15.1 16.0
ca. 17.2
ca. 18.0
ca. 22.8

Fe2 O3 , wt %
0.004
0.006 0.008
0.006 0.008
< 0.01
< 0.01
< 0.02

Insoluble material, wt %

0.04
0.04
0.03
< 0.03
ca. 0.03

Basicity * , %
1
0.1 1.0
0.1 1.0
0.1 1.0
0.8 1.5
1.0 1.8

* Dened in text

present, an alkaline substance that also has a dispersing effect, such as lime or sodium aluminate,
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, deodorizing of
mineral oils, tawing, and producing aluminum
hydroxide gel employed, for example, as a ller
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. Aluminum 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.

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 reproofing wood. However, what was known at rst as
alum was not a dened substance but referred
to both alum-containing minerals and mixtures
of alum with iron vitriol. Paracelsus was the
rst to distinguish true alum from iron vitriol. In

the years 1776 1798, Chaptal and Vauquelin

established that alum was a double salt of potassium 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 economically 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)+
(cation 2)3+ (anion2 )2 12 H2 O. The most
useful alums are those with trivalent aluminum
cations and sulfate anions, M+ Al3+ (SO2
4 )2
12 H2 O. The individual components of the alum
can be replaced, retaining both the regular
crystalline form and the hydrate water. Alums
with the following trivalent metals are known:
iron, chromium, cobalt, manganese, titanium,
vanadium, gallium, indium, scandium, rhodium, and iridium. The monovalent component
can be an alkali metal, or it can be ammonium, alkylammonium, arylammonium, or thallium. The existence of a lithium alum is uncer-

Aluminum Compounds, Inorganic

1.2.1. Potassium Aluminum Sulfate

K2 SO4 , -Al2 O3 , and 3 K2 SO4 Al2 (SO4 )3

form at 780 C, whereas K2 SO4 , -Al2 O3 , and
K2 O 12 Al2 O3 are produced at 1400 C. When
heated above its melting point, potassium alum
dehydrates, 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 puried more easily than
other aluminum salts by recrystallization 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 H2 O, occurs in nature as lowigite. 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.

Potassium aluminum sulfate [7784-24-9],

known as potassium alum, KAl(SO4 )2 12
H2 O,
1.75 g/cm3 , M r 474.4, and ammonium
aluminum sulfate are the aluminum compounds
known longest. Potassium alum occurs in nature
as eforescence on alum shale and in volcanic
areas on trachyte and lava as feather alum.
Potassium alum crystallizes in large, colorless, 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
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 contradictory. Investigations on thermal decomposition
are given in [23]. According to these results,

Production. Aluminum hydroxide (wet hydrate; Al2 O3 ca. 57 %, Fe2 O3 0.016 0.023 %,
H2 O 42.5 %) and sulfuric acid (
1.6 g/cm3 ;
Fe2 O3 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 Be with mother liquor. After ltration
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 % Fe2 O3 , 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

tain. Known combinations include potassium

aluminum, cesiumaluminum, potassiumchromium, and hydroxyammoniumaluminum. A
selenate alum also is known: KAl(SeO4 )2 12
H2 O.
All alums crystallize in strongly refracting
octahedra or cubes [1]. They have an astringent taste and rot-proong, 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 (H2 O)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.

Aluminum Compounds, Inorganic

Table 3. Solubility of some aluminum alums as a function of temperature (grams of anhydrous salt per 100 g water)
t, C
0
Sodium
56.2
Potassium 3.0
Ammonia 2.6
Rubidium 0.71
Cesium
0.2
Thallium
3.05

10
60.5
4.0
4.5
1.09
0.3
4.4

20
61.5
5.9
6.6
1.40
0.4
6.2

30
66.7
7.9
9.0

40

50

60

70

80

90

100

11.7
12.4
3.1
0.8
12.6

17
15.9
4.98
1.24

25
21.1

40
26.9

71
35.2
21.6
5.3

109
50.3

154
70.8

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.
1.2.2. Ammonium Aluminum Sulfate
Ammonium aluminum sulfate [7784-26-1], also
called ammonium alum, NH4 Al(SO4 )2 12
H2 O, M r 453.33,
1.64 g/cm3 , mp 93.5 C, occurs in nature as shermigite. Crystals doped with
other alums show birefringence. The solubility
of ammonium alum in water is similar to that of
potassium alum, with which it forms a continuous series of mixed crystals. Ammonium alum
is slightly soluble in dilute acids and glycerol
but insoluble in absolute alcohol. In aqueous solution, ammonium alum is neutral.
Data on loss of water on heating are in disagreement. GelPerin and Chebotkevich [26]

22.8

26.0

have reported that water of crystallization is released in three stages: rst to give the hydrate
with 21 mol water, then to that with 3 mol water, and nally to the anhydrous product, so that
it is in fact more correct to formulate ammonium
alum with 24 mol water. Above 193 C, decomposition 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 procedure is analogous to the potassium alum process.
To obtain a quality particularly low in iron oxide
or other metal oxides (< 0.0001 % Fe2 O3 ; normal quality ca. 0.001 % Fe2 O3 ), 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 production of
very ne 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, ammonium alum has gained considerable importance as
starting material for the production of the nely
powdered, loose aluminum oxide of high purity that is required for synthesizing corundum
gems, such as rubies and sapphires. This quality

Aluminum Compounds, Inorganic

of aluminum oxide is made by heating ammonium alum (or ammonium aluminum selenate
alum) to 1000 C.
1.2.3. Sodium Aluminum Sulfate
Sodium aluminum sulfate [7784-28-3], sodium
alum, NaAl(SO4 )2 12 H2 O, 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 ne crystalline form) is not available
commercially. These two facts make it difcult
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, sodium alum is still utilized in relatively
large quantities (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 dilution to 30 Be and subsequent heating, a sludge
of potassium sulfate, sodium silicate, and caustic
soda is added to improve the purity of the product. 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 evaporator and concentrated to such an extent that it
solidies to a hard cake on pouring into a cooling
tank. This sodium alum cake is then heated and
nally 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.

2.1. Sodium Aluminate

Sodium aluminate [1302-42-7] is an important commercial inorganic chemical. It func-

tions as an effective source of aluminum hydroxide for many industrial and technical applications. Commercial 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 , Na2 O Al2 O3 , or Na2 Al2 O4 . Commercial grades, however, always contain more
than the stoichiometric amount of Na2 O, the excess being on the order of 1.05 to 1.50 times the
formula requirement. Hydrated forms of sodium
aluminate are crystallized from concentrated solutions.
Sodium aluminate has no dened 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
sodium aluminate solution obtained from the digestion process is separated from any impurities
and then concentrated to the commercial liquid
grade by evaporation. The solid product is obtained by drying the liquid.

Aluminum Compounds, Inorganic

The sinter method also has been used to produce sodium aluminate. By sintering sodium
carbonate directly with Bayer aluminum trihydroxide 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 coagulant aid to improve occulation, and for removing 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 occulation properties and coagulates other impurities
present in the water. Depending on the impurities, the conditions of precipitation can be improved by adding aluminum sulfate [27].
In construction technology, sodium aluminate is employed to accelerate the solidication 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
advantage 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 nal strength of the building. By
adding substances such as oxoacids [29], sugar,
naphthene [30], K2 CO3 , or Na2 SO4 [31] the
nal strength increases without affecting the
setting rate signicantly. Sodium aluminate increases the resistance of mortar to water, alkali, and acid. For the production of expanded
concrete, sodium aluminate serves to activate
nitrogen-releasing substances [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
principal sources of alumina of the preparation
of alumina adsorbents and catalysts.

Table 4. Acceleration of setting by sodium aluminate in a mixture

of 6 parts sand, 2 parts concrete, and 1 part water
% NaAlO2 in concreteSetting started
0
4 h 30 min
1
30 min
1.5
15 min
2
10 min
10
instantly

Setting completed
6h
1 h 40 min
30 min
15 min

In the paper industry, sodium aluminate increases the opacity [37], retention of bers and
lling 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 rmly
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 waterinsoluble oor waxes [47], as a dispersion agent
for production of high-purity asbestos [48], as an
additive to drilling uids [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 bers; 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 Al2 O3 [12254-17-0], mp 1915 C;
BaO Al2 O3 [12004-04-5], mp 1815 C; and 3
BaO Al2 O3 [12004-05-6], mp 1425 C [50].
The rst two crystallize hexagonally.
Barium aluminates are produced by melting bauxite with coal and barite. Leaching the
melt gives a solution of barium aluminate, from

10

Aluminum Compounds, Inorganic

which the salt is obtained by evaporation. Very

pure barium aluminates can be produced by sintering mixtures of aluminum oxide with barium carbonate. All barium aluminates, including such hydrated compounds as BaO Al2 O3
4 H2 O, 2 BaO Al2 O3 5 H2 O, BaO Al2 O3
7 H2 O, and 7 BaO 6 Al2 O3 36 H2 O, hydrolyze in water, forming hydrargillite (gibbsite),
Al(OH)3 , and relatively soluble barium hydroxide.
Barium aluminate is used for purifying water
because the Ba2+ ion precipitates both the sulfates 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
production 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 soluble in alcohols. Hydrolysis with water occurs readily, giving aluminum hydroxide
and the corresponding alcohol. For a general
review of aluminum 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 impregnate textiles, as intermediates in the production of pharmaceuticals, and as antitranspirants in cosmetics. 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, M r 204.25,
mp 118 C, bp 125 130 C at 533 Pa,

d20
4 1.0346, ash 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 reux in
a column lled with aluminum chips; no catalyst
was required and nearly quantitative conversion
was obtained. The alkoxide can be puried by
distillation. In an alternative production method,
excess isopropyl 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 ltering off the
ammonium chloride that precipitates.
Aluminum sec-butoxide
[2269-22-9],
Al(OC4 H9 )3 , is a colorless liquid, M r 246.3, bp

180 C at 533 Pa, d20

4 0.9671, ash point 26 C,
and is produced in a manner similar to aluminum
isopropoxide.

4. Aluminum Chloride
4.1. Anhydrous Aluminum Chloride
Oerstedt rst 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, Al2 Cl6 . Dissociation of the dimer progresses with rising temperature 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 properties of anhydrous aluminum
chloride [55]:
Mr
 at 25 C
Sublimation temperature
at 101.3 kPa
Triple point, at 233 kPa
Heat of formation at 25 C
Heat of sublimation of dimer
at 25 C
Heat of fusion
Heat of solution at 20 C

133.34
2.44 g/cm3
181.2 C
192.5 C
705.63 0.84 kJ/mol
115.73 2.30 kJ/mol
35.35 0.84 kJ/mol
325.1 kJ/mol

Aluminum Compounds, Inorganic

Chemical Properties. Anhydrous
aluminum chloride reacts extremely violently
with water, evolving hydrogen chloride. The
hexahydrate [7784-13-6], AlCl3 6 H2 O, M r
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 concentrating the solution and calcining the hydrate. When aluminum chloride
is heated with -alumina, aluminum oxychloride, AlClO, forms, but this reaction goes in the
reverse direction at temperatures above 700 C:
AlCl3 +Al2 O3
3 AlClO

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 decomposes 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 signicance, 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,
hydrogen sulde, sulfur dioxide, sulfur tetrachloride, 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 economic signicance 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 reaction is highly exothermic:

2 Al (s) +3 Cl2 (g) Al2 Cl6 (s) H

11

= 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 difculty 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 aluminum
chloride is withdrawn from the condenser walls
at regular intervals, ground (insuring exclusion
of moisture), and classied by sieving. Chlorine
in the off-gas is removed by conventional 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
reactor 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 charcoal
catalyst. The gaseous reaction mixture enters a
brick-lined, uidized-bed reactor, where it reacts
with nely divided -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 lining has a long life.
The aluminum chloride vapor is ltered
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 removed by scrubbing, and the phosgene
is hydrolyzed with water. Extremely pure aluminum chloride is obtained by resublimation
from molten sodium aluminum chloride.
4.1.3. Quality Specications and Analysis
Anhydrous aluminum chloride is ground and
marketed as powder or granules. Aluminum is

12

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,
anhydrous aluminum chloride is classied 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 classication, packaging, 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
lter 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
petrochemical industries [58, 59]. A principal
application 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
also catalyzes the liquid-phase ethylation of benzene 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 signicantly decreased because of the
declining 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 pigments,
such as phthalocyanine green. A further application of aluminum chloride is as a nish for titanium dioxide pigments, which are in this way
protected from oxidation by an oxide layer.
Until 1960, aluminum chloride was used extensively in petroleum rening 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 compounds, such as aromatic aldehydes, ketones,
and 2-phenyl-ethanol, used in fragrances. Other
applications for anhydrous aluminum chloride
include the production of aluminum borohydride, lithium aluminum hydride, as well as
compounds of phosphorus and sulfur.
Most of these reactions with aluminum chloride produce a solution that is often used as a
occulating agent in the treatment of waste water.
Aluminum chloride also is an intermediate in
the production of aluminum by the Alcoa smelting process [60] ( Aluminum).
Data on the consumption of anhydrous aluminum chloride in the USA are given in Table
5.
Table 5. U.S. anhydrous aluminum chloride consumption in 1993
(not including the amounts consumed in the production of
aluminum) [61]
Alkylate detergents
Ethylbenzene
Hydrocarbon resins
Pharmaceuticals
Titanium dioxide
Miscellaneous
Total

2200 t
4000 t
3900 t
4000 t
2200 t
4900 t
21200 t

Aluminum Compounds, Inorganic

13

4.2. Aluminum Chloride Hexahydrate

Properties. The white hydrate AlCl3 6
H2 O [7784-13-6], M r 241.43, crystallizes
hexagonally and dissolves exothermally in water (133 g hexahydrate per 100 g water at 20 C)
[62]. The solubility increases only slightly with
temperature. The aqueous solutions are strongly
acidic because the salt hydrolyzes. Hydrogen
chloride is evolved on heating concentrated solutions. The structure of aqueous solutions of
AlCl3 6 H2 O is discussed in [63].
Production and Uses. Aqueous solutions of
AlCl3 6 H2 O can be obtained by dissolving
aluminum hydroxide in hydrochloric acid: the
hexahydrate crystallizes when hydrogen chloride 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, aluminum chloride hydroxides, poly(aluminum
hydroxychlorides), have the general formula
Al2 (OH)6n Cln x H2 O. The individual compounds are best dened either by the molar
ratio of aluminum to chloride (2/n) or by their
basicity, dened as (1 n/6) 100 %. Below a
minimum water content, which depends on n,
the compounds are unstable; they decompose
to aluminum hydroxide and aluminum oxide on
heating to above 80 C, releasing water and hydrogen chloride. All basic aluminum chlorides
with n = 1 5 can be isolated, and all are white,
in some cases crystalline substances, partially
soluble in the lower alcohols [66, 67], but readily
soluble in water. For example, 170 g of the compound Al2 (OH)5 Cl 2.5 H2 O dissolves in 100
g water at 20 C. However, the viscosity of the
solution prevents further amounts from dissolving. The electrical conductivities of the aqueous
solutions, shown in Figure 2, are characteristic
of the basic aluminum chlorides.

Figure 2. Electrical conductivity of freshly prepared basic aluminum chloride solutions: ) from Locron L (ca.
50 % aqueous solution of Al2 (OH)5 Cl 2.5 H2 O) and hydrochloric acid at constant aluminum oxide concentration
(11.5 %) and 20 C; ) prepared directly from AlCl3 6
H2 O

Aqueous solutions of basic aluminum chlorides are acidic because the compounds hydrolyze (see Table 6). The stability of the solutions
depends on the basicity: compounds with aluminum 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 approximate composition Al2 (OH)5 Cl 2
3 H2 O [12042-91-0] are so stable at concentrations > 50 % that no decomposition occurs, even
on boiling for days.
Table 6. pH values of aqueous solutions of Al2 (OH)5 Cl 2.5 H2 O
at 20 C (mass fractions, w, in %)
w
60
30
15
10
5
3

pH
3.4
4.0
4.2
4.3
4.4
4.4

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

14

Aluminum Compounds, Inorganic

glassy masses. When solutions in the basicity

range 30 65 % are evaporated, the compound
Al2 (OH)3.7 Cl2.3 6.05 H2 O (basicity 62 %) always crystallizes [69]. On addition of alkali to
basic aluminum chlorides, aluminum hydroxide
precipitates. Hydrochloric acid converts all basic aluminum chlorides to the hexahydrate:
Al2 (OH)5 Cl+5 HCl+7 H2 O2 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 signicant 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
[Al13 O4 (OH)24 (H2 O)12 ]7+ is present and is in
equilibrium with its polymeric forms. Variations
observed in the properties of these aqueous solutions 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 determined 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 ethylenediaminetetraacetate, 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 backtitrated 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
aluminum hydroxide [77] must be used. However, the preferred method is to dissolve aluminum in hydrochloric acid either thermally or
electrochemically:

2 Al+HCl+5 H2 OAl2 (OH)5 Cl+3 H2

This method is exemplied by the following

process [78]:
Aluminum electrodes are set up at distances
of 40 mm in a corrosion-resistant electrolysis
cell. Hydrochloric acid (
1.04 g/cm3 ) is poured
into the cell at a rate such that the reaction temperature remains at ca. 80 C. After all the hydrochloric acid has been added, the voltage between the rst 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
explosion 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 consists of a solution containing aluminum
and chloride in the molar ratio 2 : 1, corresponding to a basicity of 83 %. The corresponding bromides 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 H2 O [86].
Uses and Quality. The most important basic 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 occulating agent
for purifying water. In water treatment PAC can
be used for purifying surface water, sewage, and
wastewater from industry and municipalities and
for water treatment in swimming pools. A second important application for PAC is as xing
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.
Another important basic aluminium chloride
has the composition Al2 (OH)5 Cl 2 3 H2 O
and is known in the literature as aluminum
chlorohydrate. Very stringent purity specications apply to this substance. The maximum levels permitted are Fe 100 ppm, SO4 500 ppm,

Aluminum Compounds, Inorganic

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 bers
based on Al2 O3 , as a hydrophobic agent for impregnation of cotton textiles, for tanning leather,
as a retention agent in paper production, as a
binding agent for re-resistant ceramic products
as a hardening agent for rapid xing baths in the
photographic industry and as a ucculant for purifying swimming-pool water.

5. Toxicology
Aluminum sulfate is classied 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 aluminum 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
difculties 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)5 Cl 2 3 H2 O in the cosmetic industry worldwide over more than 30
years has shown that this compound is not irritating to the skin in the concentrations used commercially. Although intermittent application of
150 mg Al2 (OH)5 Cl 2 3 H2 O 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
H2 O caused the same degree of irritation [85].

4.

5.
6.
7.
8.
9.
10.

11.
12.

13.
14.
15.

16.
17.
18.
19.

20.
21.
22.
23.

24.
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