Malaysian Journal of Chemistry, 2015, Vol.

17(1), 3344

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process
T. M. H. Le1*, V. T. Nguyen1, S. T. Dong2 and T. D. Nguyen3
Institute of Natural Products Chemistry, Vietnam Academy of Science and Technology
Saint Anselm College, 100 Saint Anselm Drive, Manchester, New Hampshire, 03102, USA
3
Institute for Tropical Technology, Vietnam Academy of Science and Technology
1

*Corresponding author (e-mail: huonghvc@gmail.com)

Aluminum hydroxide (gibbsite) and iron oxide (hematite) are the main components of
natural ores and industrial products. They are the basic raw materials for the production
of aluminum and steel. Thermodynamic methods were used to study the modification
of iron(III) oxide and aluminum hydroxide surfaces at different rates and conditions of
dissolution. Instrumentation utilized for this study were X-ray diffraction, field emission
scanning electron microscope and Brunauer, Emmett and Teller (BET) surface area
analysis. Data from modified samples were evaluated using these methods for source
variation with encouraging results. Experimental results indicated that after dissolving in
acid, iron oxide had cracks and grooves on its surface but aluminum hydroxides surface
had no traces. The surface-modified phenomenon was recorded in the process of making
adsorbent from red mud generated from alumina production by Bayer process at Tan
Binh and Tan Rai Chemical Plants. BET analysis showed that the specific surface area of
red mud at Tan Binh and Tan Rai Chemical Plants dissolved in acid at a dissolution rate
of 10% which increased by 50% and 90%, respectively.
Key words: Aluminum hydroxide; iron oxide; dissolution; separation; solid phase
surface; adsorbent; red mud
Received: November 2014; Accepted: May 2015
Red mud is an insoluble residue produced
when refining of bauxite to finally obtain pure
aluminum. In Vietnam, red mud is a waste from
the production of alumina by Bayer process,
causing an alarming threat to the environment due
to its large quantity, high alkalinity and toxicity.
Many research and development activities are
going on throughout the world to study the
dissolution mechanism of red mud [1,2]. The
major composition of Tan Binh bauxites residue
is: Fe2O3, 47.74% and Al2O3, 18.19%. Therefore,
as an effective utilization of bauxite residue,
red mud is widely used to recover metallic
components and make adsorbents [1, 2].
Adsorbent can be made by mixing red mud in
acid to remove residual sodium and increase the

activity of the surface [1, 2]. However the surface

change during the acid treatment has not been
clarified. Dissolution mechanism of aluminum
and iron in red mud has not been studied enough.
Our present research deals with the modification
of solid phase surface in the dissolution process of
iron oxide and aluminum hydroxide in a separate
system and in the red mud system.
EXPERIMENTAL
Materials
Pure iron oxide was provided by SLGH (China).
Pure aluminum hydroxide and red mud were
provided by the Tan Binh Chemical Plant
(Vietnam). Red mud samples were supplied by
Tan Binh and Tan Rai Chemical Plants.

34 Le, T.M.H. et al.

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

Instrumentation

samples at dissolution rates of 10%, 20%, 30%,

40% and 50%. (This is done by taking 10%, 20%,
30% .40%, 50% of the acid that is necessary to
disolution the whole of the aluminum and iron in
red mud). The system was heated to boil at 98C.
Samples were diluted in purified water to 100 ml
to fix the ratio of liquid to solid at 5:1 (100 ml
solution: 20 g sample).

The structure of untreated sample was analyzed by

Siemens D5000 X-ray Powder Diffraction. SEM
images were captured with an Hitachi S-4800
field emission scanning electron microscope and
Brunauer, Emett and Teller (BET) results were
measured with a Micromeritics TriStar 3000.
Procedure
Particle size of all samples ranged from 0.041 to
0.22 mm. Approximately 20 g of each sample was
added to the reaction system. Red mud samples
were dried at 70C for 5 h and sieved to break
down the adhesion between particles.
Dissolution process was carried out in a 250
ml spherical flask in a bain-marie heated at 90C
and stirred by an agitator at a stirring rate of 480
rpm. To examine the effect of dissolution rate on
surface change, approximately 20 g of iron(III)
oxide and aluminum hydroxide samples were
dissolved in 100 ml sulphuric acid at different
concentrations from 0.2 M to 2.2 M to dissolve

The mixture was allowed to react for 2

h; at which point the solution was filtered.
Experimental dissolution rates were re-examined.
Iron and aluminum contents in the leach solutions
were determined complexometrically by EDTA
titration. The solid residue was dried at 70C
for 5 h and SEM and BET measurements were
performed on it.
RESULTS AND DISCUSSION
Dissolution Reactions
Red mud was digested with sulphuric acid and the
reactions in the medium were as follow:

2Al(OH)3 + 3H2SO4 Al2(SO4)3 + 6H2O

(1)

Fe2O3 + 3H2SO4 Fe2(SO4)3 +3H2O

(2)

Modification of Iron(III) Oxides Solid Phase

Surface in Dissolution Process
Analysis of structure and dissolution mechanism of Fe2O3 in sulphuric acid. By taking the
samples X-Ray diffraction (Figure 1) and comparing its result with the standard diffraction, the
result showed that the structure of the sample
contained 96.21% hermatite. Hematite is by far
the most common form of iron oxides, having
important magnetic properties. In hematite
structure shown in Figure 2, oxygen ions are
hexagonally close packed, and iron is present only
in octahedral sites. Dissolution rates for hematite
in H2SO4 have been reported to decrease for acid

concentrations above 7 M. Hematite structure is

dense, having a density of 5.26 g/cm3 and does
not contain cation vacancies. The high density
along with the occurrence of iron atoms solely in
octahedral sites may be responsible for the slow
dissolution of hematite in acid [4].
Iron oxide sample was prepared and dissolved
in sulphuric acid at different dissolution rates as
described in the experimental section. The diluted
solution was titrated to determine the excess
quantity of acid and iron. The result was used to
evaluate the experimental dissolution level. The
dissolution level is described in Table 1.

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

35 Le, T.M.H. et al.

1200
1100
1000
900

Lin Cps)

800
700
600
500
400
300
200
100
0

20

30

40

2-Theta-Scale

50

Figure 1. X-ray diffraction of iron oxide.

Figure 2. Structure of hematite [4].

60

70

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

36 Le, T.M.H. et al.

Table 1. Experimental dissolution level of hematite samples.

Dissolution level
Sample expected dissolution rate
Experimental dissolution rate (%)

Hematite sample
Fe 10%

Fe 20%

Fe3+ 30%

Fe3+ 40%

Fe3+ 50%

9.64

19.42

29.34

39.32

49.40

3+

In the dissolution process, reaction rate

changes if Fe2+ ions exist in the solution. The
reaction rate of the system is described in
Equation 3 [5].

3+

This paper focuses only on explaining

the principle of solid phase surface, not the
electrochemical processes that occurrs in the
dissolution process.

Wi = K[H]m[Fe(II)](1+) z+[Fe(III)](1+) z+

Although the oxide particles in untreated

system were not distributed uniformly in terms of
size and geometry, they link together (Figure 3A).
At a dissolution rate of 10%, the morphological
variation of particle structure was insignificant
(Figure 3B). The reaction happened mainly at
separate surface between particles which destroyed the connection between particles to create
blocks. The variation happened at small points on
the surface of hematite particle. As the dissolution
rate increased, the links between particles were
fully broken. This phenomenon led to a rapid
formation of small-sized particles. On the surface
of larger-sized particles, grooves were formed.
This phenomenon happened due to the fact
that the structure of hematite consisted of hcp
arrays of oxygen ions stacked along the [001]
direction. Two thirds of the sites were filled with
Fe3+ ions; therefore, H+ ions could easily react
with iron atoms [5]. However, once the surface
links on large-sized oxide particles cracked,
many small particles could be formed. When
the dissolution rate reached 20% (Figure 3C), a
strong surface growth of solid phase happened.
When the dissolution rates were increased
gradually to 30% (Figure 3D), 40% (Figure 3E)
and 50% (Figure 3F), the formation of smallersized oxide particles limited the ability to
create grooves and cracks on particles surface.
Therefore, the specific surface area of solid phase
decreased as represented in the BET measurement
results (Table 2).

nn == qq (Kred)n[A]n
ii == qq (Kox)i[A]i

(3)

SEM and BET analysis of samples at different

dissolution rates indicated that the sample which
dissolved 20% in sulphuric acid had the largest
specific area. The result is shown in Figure 4. At
this dissolution rate, cracks were formed on the
surface of large oxide particles. Since the reaction
on small particles and particles that separate off
the link did not take place completely, the quantity
of small particles did not decrease considerably.
At higher dissolution rates (20%, 30%, 40%, and
50%), the specific surface area of iron oxides
solid phase started decreasing.
Modification of aluminum hydroxides
solid phase surface in dissolution process. By
taking the samples X-Ray diffraction (Figure 5)
and comparing its result with the standard
diffraction, the result showed that the structure
of the sample contained 79.72% gibbsite. The
schematic X-ray diffraction of the aluminum
hydroxide sample (Figure 5) showed that the main
component of aluminum hydroxide was gibbsite.
Gibbsite has layered structure. The layers of
gibbsite are connected by weak hydrogen bonds
(Figure 6). Each layer consists of two planes of
approximately close-packed oxygen, enclosing a
plane of aluminium. Aluminum ions occupy twothirds of the octahedral holes between the two
layers [6].
Gibbsite dissolution rate is very high in
sulphuric acid compared to its dissolution rate in

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

37 Le, T.M.H. et al.

Figure 3. A: SEM images of untreated hematite sample; (B), (C), (D), (E), (F): SEM images of hematite at
dissolution rate of 10%, 20%, 30%, 40% and 50%, respectively.

Table 2. Surface area of hematite samples at different dissolution rates

Dissolution level

Hematite sample

Sample expected
dissolution rate

Untreated Fe2O3

Surface Area (m2/g)

3.8813

Fe 10% Fe3+ 20% Fe3+ 30% Fe3+ 40% Fe3+ 50%

3+

4.3718

4.9394

4.1314

3.8623

3.6892

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

38 Le, T.M.H. et al.

Figure 4. SEM image of hematite dissolved in 20% sulphuric acid at 10 000x magnification.

Lin (Cps)

1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0

20

30

40

2-Theta-Scale

50

Figure 5. X-ray diffraction of aluminum hydroxide.

60

70

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

39 Le, T.M.H. et al.

other acids such as perchloric acid, hydrochloric

acid [9]. The dissolution of gibbsite occurs on the
edges of unit layers rather than on basal faces [10].
This is due to the unstable bonding of OH groups
on the edges of the unit layer [11].
Aluminum hydroxide sample was prepared
and dissolved in sulphuric acid at different
dissolution rates as described in the experimental
section. Diluted solution was titrated to determine
the excess quantity of acid and aluminum. The
result was used to evaluate the experimental
dissolution level (Table 3).

Al atoms

The following results were inferred from SEM

images of solid phase of aluminum hydroxide in
dissolution process:
The structure of gibbsite is hexagonal crystal
and stacked. The corner and edge of
aluminum hydroxide could be observed in
Figure 7A. With this structure, the reaction
between Al(OH)3 and sulphuric acid in
dissolution process occured mainly at the
angular position of this structure, not on
the surface like in the reaction between
Fe2O3 and sulphuric acid. At dissolution

OH lower layer

OH upper layer
a
Figure 6. Structure of Gibbsite [4, 5].

Table 3. Experimental dissolution level of aluminum hydroxide.

Dissolution rate

Aluminium

Sample expected dissolution rate

Al 10%

Al 20%

Al3+ 30%

Al3+ 40%

Al3+ 50%

Experimental dissolution rate (%)

9.83

19.70

29.10

39.72

49.70

3+

3+

40 Le, T.M.H. et al.

rate of 10%, reaction between Al(OH)3

and acid occured at angular positions, making the surface of the crystal to change
significantly (Figure 7B). The angles and
corners were flattened. When the dissolution
rate reached 20% (Figure 7C), this process
occured more intensely. The separation

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

between layers could be observed on the

surface of the crystal.
When dissolution rate reached 30% (Figure
7D) and 40% (Figure 7E), layers in the
crystal structure were divided at more
frequent rates. Along with the edges and

Figure 7. A: SEM image of untreated gibbsite sample; (B), (C), (D), (E), (F): SEM images of gibbsite at
dissolution rates of 10%, 20%, 30%, 40% and 50%, respectively.

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

41 Le, T.M.H. et al.

corners of the crystals, other positions on

the surface of the particles began to react.
These additional positions resulted in
the formation of capillaries in hole form.
However, if the level of dissolution kept
increasing, this phenomenon stopped taking
place. BET results in Table 5 showed that
Al(OH)3 samples which dissolved 30% in
sulphuric acid had the largest specific surface
area. Specific surface area of Al(OH)3 was
reported to decrease at dissolution rate
above 30%.
In single systems, the modification of solid
phase followed a general rule. The specific surface
area of solid phase surface increased until the solid
phase particles reacted so intensely that the particle
size started shrinking. The particle surface was not
large enough to form cracks or layers, resulting in
a decrease in specific surface area.
Modification of Red Muds Solid Phase
Surface in Dissolution Process

Lin (Cps)

Dissolution of aluminum hydroxide and

iron(III) oxide in red mud system. According to
Figure 8 and database, the main components of red
mud are gibbsite and hematite. Red mud samples
2000
1900
1800
1700
1600
1500
1400
1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0

10

20

underwent dissolution process at dissolution

levels of 10%, 20% and 30% with the same
conditions as aluminum hydroxide and iron(III)
oxide. Compositions of the solution and of the
solid phase after dissolution are shown in Table
4 and Figure 9. There is competition in terms of
speed between components in red mud system.
The reaction rates of gibbsite and hematite with
acid are different, making the ratio between Al3+
and Fe3+ in the residue varies. Also, due to the
difference in reaction rate, the growth of red mud
particles surface does not follow the rules applied
for separated system [12]. Especially, layered
separation of aluminum cannot be observed due
to the tiny size of gibbsite particle and its equal
dispersion into the solid phase of red mud particles.
Modification of red mud particles in dissolution
process. BET results of red mud samples at
different dissolution rate are shown in Table 5.
According to SEM images and BET
measurement results, Tan Binh red mud samples
dissolved at dissolution rates of 10% and 20%
with a strong growth on surface properties. For
Tan Rai red mud, the samples dissolved at 10%
and had a strong growth on surface properties. This

30

40

2-Theta-Scale
Figure 8. X-ray diffraction of Tan Binh red mud [11].

50

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

42 Le, T.M.H. et al.

Table 4. Dissolution efficiency and solid phase composition of Tan Binh red mud in.
Dissolution efficiency

Composition of solid phase

Sample expected
dissolution rate

Fe (%)

Al (%)

Fe2O3 (%)

Al2O3 (%)

Untreated red mud

47.73

18.19

Red mud 10%

0.35

21.24

42.68

27.2

Red mud 20%

1.9

31.88

39.58

24.93

Red mud 30%

13.07

79.6

19.13

12.08

3+

3+

Table 5. Specific surface area of red mud at different dissolution rates.

Red mud
disolution rate

Specific surface area of Tan Binh red mud

(m2/g)

Specific surface area of Tan Rai red mud

(m2/g)

Red mud 0%

105.4

54.68

Red mud 10%

154.7

100.91

Red mud 20%

150.8

95.59

Red mud 30%

142.5

91.56

Red mud 40%

137.1

85.50

Figure 9. SEM images of red mud images at dissolution rate of (A) 10%, (B) 20%, and (C) 30%.

Characteristics of Surface-modified Aluminum Hydroxide,

Iron Oxide and Red Mud in Dissolution Process

43 Le, T.M.H. et al.

observation demonstrated the ability to compete

between different components to react with acid.
Red mud surface formed capillaries without
causing debris or corrosion. The reaction rate with
sulphuric acid of [Al3+] was faster than that of
[Fe3+] ion. Therefore, in solid phase of red mud
after dissolution process, the surface properties
developed and the ratio between aluminum and
iron varied as the composition of iron in the
residue increased. Thanks to these characteristics;
red mud particles modified by this method have
good adsorption abilities [13, 14].
Applications of adsorbents made from red
mud. To test the absorption capacity of the
above Tan Binh red mud experiments were
conducted with ion Ni(II) and As(III, V) from the
substance NiSO4 and As2O3 respectively [13]. The
experiments were carried out in room temperature
conditions with 1 g volume of adsorbent, pH of
67 for Ni(II) and As(III,V). Adsorption time was
2 h and the concentration of adsorbed solutions
was checked by standard colorimetric method.
The absorption capacity results of red mud are
shown in Table 6.
The development of aluminum hydroxide and
iron(III) oxides specific surface when dissolving
in sulphuric acid at different dissolution rates
provides valuable information about surface
growth within dissolution process. From the law
of surface variation, we aim to continue testing
to find out the optimum conditions for making
adsorbents from red mud and other minerals
containing aluminum hydroxide and iron oxide.
CONCLUSION
In red mud system, dissolution of Al(OH)3 in
sulphuric acid happened in the form of layer
separation. When iron (III) oxide was dissolved
in acid, the solid phase surface had grooves and

cracks in all directions. In single systems of Al3+

and Fe3+, when the surface growth increased
along with the increase in dissolution rate to a
limiting value, there was a formation of smaller
particles. The solid surface could not be separated
into layers and grooves, resulting in a decrease in
specific areas.
The modification of red mud surface within the
dissolution process did not follow the principles
applied for single systems due to the differences
in the level of competition and reaction rate. There
was a development in specific surface of particles
for solid phase after the sample was dissolved.
The development of this surface characteristics
enabled dissolved red mud particles to have
typical features of adsorbent. Specific surface area
of Tan Binh and Tan Rai red mud dissolved in acid
at dissolution rate of 10% increased by 50% and
90%, respectively. However, to confirm adsorption
capacity, more research needs to be conducted on
the characteristics of electrical properties of solid
phase surface.
The results of research on red mud confirmed
the potential of applying dissolution process for
the manufacture of adsorbent from red mud and
the recycling of red mud to reduce environmental
pollution. Also, red mud can be integrated with
the manufacture of flocculants with the secondary
wastes treatment process [13].
ACKNOWLEDGEMENTS
The authors would like to express their sincere
appreciation to the project Processing Technology of Red Mud from Taynguyen Bauxite code
named 05/HD-DT.13/CNMT of the programme
on scientific research, application and technology
transfer to develop the environmental industry
(Ministry of Industry and Trade of the Socialist
Republic of Vietnam).

Table 6. Ion adsorption capacity of adsorbents made from red mud [13].
Ion
Ni

2+

As (III, V)

Adsorption Capacity (mg/g)

Tan Binh red mud 10% dissolved

Tan Binh red mud 30% dissolved

19.2

35.8

0.79

44 Le, T.M.H. et al.

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