Clay Minerals, (2012) 47, 31–44

Characterization of natural- and organo-

bentonite by XRD, SEM, FT-IR and
thermal analysis techniques and its
adsorption behaviour in aqueous solutions
G . A . I K H T I Y A R O V A 1 , A . S . Ö Z C A N 2 , Ö . G Ö K 2 AND A . Ö Z C A N 2 , *
1
Department of General Chemistry, Faculty of Natural Science, Bukhara State University, 705017 Bukhara,
Uzbekistan, and 2 Department of Chemistry, Faculty of Science, Anadolu University, 26470 Eskis ehir, Turkey

(Received 25 April 2011; revised 10 August 2011; Editor: John Adams)

AB ST R ACT : In this study, natural bentonite was modified with hexadecyltrimethylammonium

(HDTMA) bromide to obtain organobentonite (HDTMA-bentonite). Bentonite and HDTMA-
bentonite were then characterized using XRD, XRF, SEM, FT-IR, thermogravimetric (TG) analysis,
elemental analysis and Brunauer-Emmett-Teller (BET) surface area techniques. The HDTMA+
cation was found to be located on the surface and enters the interlayer spaces of smectite according to
the XRD and SEM results. FT-IR spectra indicated the existence of HDTMA functional groups on
the bentonite surface. The BET surface area significantly decreased after the modification due to the
coverage of the pores of natural bentonite. After the characterization, the adsorption of a textile dye,
Reactive Blue 19 (RB19), onto bentonite and HDTMA-bentonite was investigated. The maximum
adsorption capacity of HDTMA-bentonite for RB19 was 502 mg g1 at 20ºC. The adsorption process
followed a pseudo-second-order kinetic model and it was exothermic and physical in nature.

KEYWORDS: bentonite, organobentonite, modification, characterization, adsorption, reactive dye.

Bentonite is a clay mainly composed of smectite
group clay minerals which is made up of two silica
tetrahedral sheets with a central Al octahedral sheet.
It has a permanent negative charges that arises from
the isomorphous substitution of Al3+ for Si4+ in the
tetrahedral layer and Mg 2+ for Al 3+ in the
octahedral layer. This negative charge is balanced
by the presence of exchangeable cations (Na+, Ca2+,
etc.) on the clay surfaces (Grim, 1968). In aqueous
solutions, water molecules are intercalated into the
interlamellar space of smectite, leading to an
expansion of the mineral. The bentonite obtained
is inherently hydrophilic in nature because of the
* E-mail: aozcan@anadolu.edu.tr
DOI: 10.1180/claymin.2012.047.1.31
hydration of metal ions. Therefore, hydrated
bentonite is an ineffective adsorbent for hydro-
phobic molecules but can be transformed into a
hydrophobic form via an ion-exchange mechanism
by modifying it with long-chain quaternary amine
cations (surfactants) to obtain organobentonite.
(Özcan & Özcan, 2004; Özcan et al., 2004a,b;
Shen, 2001; Sheng et al., 1996). This leads to
increase in the adsorption capacity compared with
natural bentonite and it can be effectively used as
an adsorbent for the adsorption of dyes.
Natural bentonite and organobentonite can be
characterized by XRD, XRF, SEM, FT-IR, thermo-
gravimetry (TG), elemental analysis, and Brunauer-
Emmett-Teller (BET) surface area techniques.
X-ray diffraction analysis (XRD) was conducted
to evaluate the changes that occur in the
interlamellar distance of smectite as a result of

# 2012 The Mineralogical Society

32 G. A. Ikhtiyarova et al.
their interaction with organic dye molecules.
Intercalation of a larger size of the surfactant
cations compared with that of the replaced cations
among layers of clay minerals not only changes the
surface properties from hydrophilic to hydrophobic,
but also greatly increases the interlamellar distance
(basal spacing) of the layers, thus easing the
attraction of organic textile dye molecules. The
alkylammonium cations (surfactants) in smectite are
arranged in monolayers, bilayers and pseudotrimo-
lecular arrangements, as well as forming a paraffin-
type structures in the interlayer. Clay minerals are
known to vary their interlayer distances depending
on the nature of the intercalated molecules and their
microscopic orientation. Interaction of smectite
layers with a long-chain surfactant on external
surfaces or crystal edges was conceivable (Xi et al.,
2004; Yariv, 2004; Lee et al., 2005; Komadel,
2003). Scanning electron microscopy (SEM) also
shows the interaction between the surfactant
molecules and bentonite particles. Fourier transform
infrared spectra (FT-IR) were taken to observe
functional groups of natural bentonite and surfactant
modified bentonite. Often, the combination of both
the thermogravimetric (TG) and differential thermo-
gravimetric (dTG) analysis curves may be used to
interpret the thermal behaviour of natural bentonite
or organobentonite. All mass loss events in natural
bentonite are associated with the loss of water.
These may be from either desorption of water, loss
of interlayer water or dehydroxylation of the silicate
lattice. The amount of water uptake of bentonite
depends on the relative humidity of the environ-
ment to which they are exposed. The BET surface
area significantly decreases when natural bentonite
is modified with a surfactant due to the coverage of
the pores of natural bentonite.
Reactive dyes are widely used in many industries
including textiles, pulp mills, leather, dye synthesis,
printing and plastics. They are the most common
dyes because of their advantages such as bright
colours, excellent colour fastness and ease of
application. The world-wide level of production and
extensive use of dyes generates coloured, toxic and
harmful wastewaters. In fact, the disposal of these
wastewaters before they make contact with unpol-
luted natural water bodies is a very important issue.
Several conventional physical, chemical and biolo-
gical treatment methods can be used for the removal
of textile effluents from wastewaters. The utility of
these techniques has been limited since many of the
textile dyes are stable to light and oxidation.
Adsorption has been proved to be the most promising
method to treat textile dye effluents because it has
many advantages over other traditional treatment
methods. It is a low-cost procedure with greater
profitability, simple to operate with easy recovery
and reuse of adsorbent and very efficient. Even
though activated carbon is perhaps the most widely
used adsorbent for the treatment of dye-bearing
wastewaters owing to its large surface area and
excellent adsorption capacity, but it has high
operation costs and it is necessary to regenerate
after each adsorption cycle. Due to the disadvantages
of activated carbon, there is a need to search low-
cost, locally available and effective alternative
adsorbent materials for the textile wastewater
treatment. Studies indicated that chitosan (Hasan et
al., 2008), peach stones (Gerçel et al., 2009), peat
(Ho & McKay, 1998a), wood (Ho & McKay,
1998b), bentonite (Al-Asheh et al., 2003; Özcan &
Özcan, 2004; Özcan et al., 2004a, 2005, 2006a, b,
2007; Hu et al., 2006; Gök et al., 2010), sepiolite
(Özcan & Özcan, 2005; Ravikumar et al., 2005;
Özcan et al., 2006a, b; Özcan & Özcan, 2008),
montmorillonite (Wang et al., 2004; Wang & Wang,
2008), zeolite (Armağan et al., 2004; Wang et al.,
2006) and smectite (Ogawa et al., 1996; Arbeloa et
al., 1998; Czı́merová et al., 2004) etc. could be used
as alternative adsorbents for the removal of textile
dye effluents from aqueous solutions.
In this study, initially natural bentonite and
hexadecyltrimethylammonium (HDTMA)-bromide-
modified bentonite were characterized using various
methods. After that, the adsorption behaviour of
Reactive Blue 19 (RB19) onto natural bentonite and
HDTMA-bentonite from aqueous solutions was
tested. The effects of temperature, pH and contact
time were examined, and the kinetics, isotherm and
thermodynamic data were also evaluated.
EXPERIMENTAL
Materials
A commercial textile dye, Reactive Blue 19
(RB19) (Remazol Brilliant Blue R) (C.I. 61200)
which is an anionic dye, was provided from Turkey
and used in all adsorption experiments without
further purification. The chemical structure of RB19
is illustrated in Fig. 1. The natural bentonite was
obtained from Çanakkale, Turkey. It was crushed,
ground, sieved through a 63 mm sieve, and then
dried at 110ºC in an oven for 2 h prior to use.
 Characterization and adsorption behaviour of bentonite
Preparation of HDTMA-bentonite
The respective quantities of hexadecyltrimethy-
lammonium bromide, which was used as a
surfactant, equal to twice the cation exchange
capacity of bentonite and a thirty gram natural
bentonite was mixed in 0.8 litres of deionized water
for the preparation of HDTMA-bentonite (Özcan et
al., 2004a,b, 2005, 2006a,b, 2007; Shen, 2001;
Sheng et al., 1996; Özcan & Özcan, 2005; Gök et
al., 2010). The prepared HDTMA-bentonite was
then washed with deionized water until free of salts
and a negative bromide test had been obtained with
0.1 M AgNO3.
Characterization
The chemical analysis of natural bentonite was
obtained using a wavelength dispersive X-ray
fluorescence (XRF) spectrometer (Bruker S8Tiger
Model, Germany). A scanning electron microscope
(SEM) was used to define the changes in the
adsorbent with modification. The crystalline phases
present in bentonite were determined by an X-ray
diffractometer (XRD-Rigaku Rint 2000) using
Cu-Ka radiation. Natural bentonite and HDTMA-
bentonite as random specimens were analysed by
X-ray powder diffraction equipment before and
after the modification procedure to observe the
intercalation of surfactant into smectite layers.
FT-IR spectra of natural and modified bentonite
prepared as KBr discs were recorded in a Perkin-
Elmer Spectrum 100 Model Infrared
Spectrophotometer to examine functional groups
of bentonite and HDTMA-bentonite. FT-IR spectra
were recorded in the range of 4004000 cm1 at a
resolution of 2 cm1.
Thermal analysis (Setaram, Labsys TG-DTA
Model) was carried out to observe whether or not
the surfactant modification of bentonite had been
FIG. 1. Chemical structure of RB19.
33
achieved. The thermal analyses for natural bentonite
and HDTMA-bentonite were recorded in the
temperature range 251000oC at a heating rate of
10ºC min 1 under an argon atmosphere.
Approximately 20 mg of finely ground sample
was heated in an open alumina crucible.
Cation exchange capacity (CEC) determination
was carried out by using methylene blue (Taylor,
1985), barium chloride and ammonium acetate
solutions (Czı́merová et al., 2006), respectively.
The elemental analysis (Vario EL III Elemental
Analyzer, Hanau, Germany) was carried out to
determine the C/N ratio in HDTMA-bentonite. The
BET surface areas of natural bentonite and
HDTMA-bentonite were determined from N 2
adsorption isotherms with a surface area analyser
(Quantachrome Instruments, Nova 2200e).
Adsorption experiments
All adsorption experiments were undertaken in a
batch technique by using a magnetic stirrer in a
thermostatic water bath. To determine the optimum
pH value, where the maximum adsorption was
achieved, 50 ml of dye solution at a concentration
of 250 mg dm3 was treated with 0.050 g natural
bentonite or 0.025 g of HDTMA-bentonite in the
100 ml Erlenmeyer flasks and then the pH of the
solution was carefully adjusted between 1.5 and 9.5
by adding a small volume of HCl or NaOH solution
using a pH meter (Fisher Accumet AB15). The
solutions were stirred for 60 min and a constant
temperature of 20ºC. Then the solution was gently
filtered and the concentration of the dye in the
solution was determined by measuring the absor-
bance by using a UV-vis spectrophotometer
(Shimadzu UV-1201). The wavelength was
recorded before and after the adsorption and in all
cases no shift in the absorbance peak (lmax = 592
nm) was observed. The optimum pH was then
identified as 1.5 and used throughout all adsorption
experiments, which were conducted at various time
intervals and temperatures (20, 30 and 40ºC) to
determine when equilibrium was reached and the
maximum removal of dye was attained.
A solution of RB19 of 250 mg dm3 concentra-
tion (50 ml) for kinetic studies or
200550 mg dm 3 concentration range for
isotherm studies and 0.025 g of HDTMA-bentonite
were placed in a 100 ml Erlenmeyer flask. Keeping
the flask in a water bath and adjusting the desired
temperature, the mixture was then mechanically
34 G. A. Ikhtiyarova et al.
stirred. After fixed time intervals, the mixture in the
flask was filtered and each filtered solution was
quantitatively analysed for the adsorbed dye.
RESULTS AND DISCUSSION
Characterization of adsorbents
The chemical composition of natural bentonite was
determined by using XRF analysis and the results
obtained were as follows (wt.%): SiO2: 65.13, Al2O3:
14.41, MgO: 3.31, CaO: 1.91, Fe2O3: 0.74, K2O:
0.56, Na2O: 0.17, TiO2: 0.10 and loss on ignition:
11.21. This result indicates the presence of silica and
alumina as major constituents along with traces of
sodium, potassium, iron, magnesium, calcium, and
titanium oxides in the form of impurities. XRD also
indicated the presence of free quartz in bentonite. It
is, thus, expected that the adsorbate species will be
removed mainly by SiO2 and/or Al2O3.
The XRD patterns of natural bentonite and
HDTMA-bentonite are illustrated in Fig. 2. The
mineralogical composition of bentonite, which was
found from XRD, was determined by using its
characteristic reflections. It consists of predomi-
nantly montmorillonite (72%) (2y = 5.94, 17.54,
19.72, 29.52, 34.98 and 36.04º) and substantial
amounts of admixture of quartz (2y = 21.84, 26.66,
35.98, 39.42 and 42.40º) and cristobalite (2y =
21.84 and 31.30º).
For HDTMA-bentonite there are multiple peaks
at 19.03, 12.99, 9.71 and 5.54 Å. The first peak,
which corresponds to 4.64º 2y, is caused by the
lateral monolayer of surfactant cations present in
the interlamellar space of the adsorbent (Majdan et
al., 2009). This conclusion is justified so that the
expansion in the basal spacing of clay mineral can
be calculated as Dd = d  14.87 Å, where d is the
basal spacing of HDTMA-bentonite and Dd is
found to be 4.16 Å. This result revealed randomly
lateral-monolayer arrangements of the intercalated
alkylammonium cation into bentonite. The shape of
the perfect straight-chain quaternary ammonium
cation (HDTMA+), has the appearance of a ‘‘nail’’
where the long alkyl chain is ‘‘body’’ of the nail and
the chain end holding three methyl groups is the
‘‘nail-head’’. The theoretical length of the
HDTMA+ cation is 25 Å, and the height of alkyl
chain is 4.0 Å and the nail-head is 5.1 Å. It can be
concluded that the HDTMA + cation lies ‘‘flat’’
between the smectite layers (Zhu et al., 2003).
Although this type of HDTMA+ cation arrangement
between the structural layers of smectite is effective
at concentrations of the HDTMA+ cation close to
1 CEC, the charge heterogeneity of these clay
mineral layers, changing from layer to layer and
within the same layer, indicates that the presence of
the surfactant paraffin mono- and bilayers is also
possible (Majdan et al., 2009). The other peaks
appear at 12.99, 9.71 and 5.54 Å for more than 1.5
CEC, and it is proposed that pseudotrimolecular
layer arrangements exist as well as the monolayer
and bilayer structures. These data indicate that the
basal spacings of HDTMA-bentonite are not
uniform. When HDTMA-Br is intercalated into
the layer of montmorillonite some layers intercalate
easily with surfactant, whereas some layers do not.
Therefore different basal spacings occur (Zhou et
al., 2007). The XRD results are also consistent with
the thermal and elemental analysis results.
The SEM photomicrographs obtained for natural
bentonite and HDTMA-bentonite are illustrated in
Fig. 3. Apparently the surface of natural bentonite
was very smooth with fluffy appearance. It can be
clearly observed that natural bentonite, after a
cationic surfactant insertion reaction, loses its
foliated structure and gains more rough surface.
The micrograph of natural bentonite also shows
some deformed parts which probably occurred due
to the reduction in certain crystalline domains of
the clay particles.
The FT-IR spectra of natural bentonite and
HDTMA-bentonite (Fig. 4) were carried out over
the range 4004000 cm1 and were compared with
each other to obtain information on the modifica-
tion of bentonite with HDTMA functional groups.
The position and shape of the OH stretching
band in the FT-IR spectra of smectite minerals is
basically influenced by the nature of the octahedral
atoms to which the hydroxyl groups are coordi-
nated. A group of absorption peaks was observed
between 3624 and 3430 cm1, which is due to
OH stretching vibration bands of water in natural
bentonite (Fig. 4a) and HDTMA-bentonite (Fig. 4b)
and their bending vibrations at 916 and 912 cm1.
The absorption band at 3624 cm1, found in the
spectrum of natural bentonite, is typical for smectite
minerals with large amounts of Al in the octahedral
sheet. Another band at around 3412 cm 1
(stretching band of the OH groups) was observed;
the intensity of this band decreased with surfactant
modification (see Fig. 4) and is evidence for the
modification of bentonite with surfactant
(HDTMA-Br) functional groups.
 Characterization and adsorption behaviour of bentonite 35

FIG. 2. XRD patterns of (a) natural bentonite and (b) HDTMA-bentonite.

FIG. 3. Scanning electron microscopy (SEM) images of (a) natural bentonite and (b) HDTMA-bentonite.
36 G. A. Ikhtiyarova et al.
FIG. 4. FTIR spectra of (a) natural bentonite and (b) HDTMA-bentonite.
A pair of strong bands at 2851 and 2920 cm1
was observed only in HDTMA-bentonite (Fig. 4b)
and can be assigned to the symmetric and
asymmetric stretching vibrations of the methylene
groups (nCH2) and their bending vibrations between
1372 and 1470 cm1. This supports the modifica-
tion of natural bentonite with surfactant cations
(Madejová et al., 1994; Silverstein & Webster,
1998; Madejová, 2003), but these stretching bands
are not observed in natural bentonite (Fig. 4a). The
observed bands between 1639 and 1637 cm1 in
both of the adsorbents also correspond to the OH
deformation of water.
The FT-IR spectra of clay minerals show SiO
stretching and bending as well as OH bending
absorptions in the 1300400 cm1 range. The
SiO coordination bands at 1091 cm1 result from
the SiO vibrations of quartz and cristobalite. The
deep band at around 1040 cm1 represents the
stretching of SiO in the SiOSi groups of the
tetrahedral sheet. A primary doublet peak of
quartz near 779 and 795 cm1 was observed.
Cristobalite shows a primary peak at the same
wavenumber (795 cm1) as quartz. Since quartz,
cristobalite, opal and amorphous silica share the
same primary peak location in the FT-IR spectrum
at around 795 cm1, cristobalite can be deter-
mined using its secondary peak in the presence of
these interferences (Stuber et al., 2009). A
secondary peak of cristobalite was observed at
627 cm1 and the bending vibrations of OSiO
were found at 521 and 468 cm1. The OH
bending region of smectite minerals often provides
valuable information on the composition of the
octahedral sheets (Madejová, 2003). Two peaks at
916 (Al2OH) and 845 cm1 (AlMgOH) reflect
partial substitution of octahedral Al by Mg in
bentonite. The FT-IR results are also consistent
 Characterization and adsorption behaviour of bentonite 37

with the elemental, thermal and XRD analysis
results.
Thermal analysis curves of natural bentonite,
pure surfactant (HDTMA-Br) and
HDTMA-bentonite are illustrated in Fig. 5ac.
The thermogravimetric (TG) analysis curve related
to the natural bentonite (Fig. 5a) shows mass losses
of 6.23 and 5.80% in the temperature ranges
25200ºC and 600800ºC respectively. The two
endothermic peaks in the differential thermogravi-
metric (DTG) analysis curve of natural bentonite in
the range 25200ºC denote the release of different
water species coordinated to the interlayer cations
and to the surface humidity. The third endothermic
peak in the temperature region 600–800ºC relates to
the dehydroxylation of the layer silicate minerals
and the elimination of structural OH groups. The
TG curve related to the surfactant modified-
bentonite (Fig. 5c) exhibited mass losses of 0.70%
at 25200ºC, 34.04% at 200-400ºC and 2.94% at
600800ºC which are due to the thermal evolution
of moisture and interlayer water and the thermal
oxidation of the surfactant cation and structural
OH groups respectively. The intensity of the DTG
peaks for HDTMA-bentonite in the temperature
region 25100ºC was lower than that in the DTG
curve of unmodified natural bentonite due to the
hydrophobic nature of this sample as can be seen
from Fig. 5a and c. Two DTG peaks between 250
and 420ºC were observed in HDTMA-bentonite
(Fig. 5c) and they confirm the modification of
bentonite with surfactant, but these peaks are not
observed in natural bentonite (Fig. 5a). The
complexity of the thermal decomposition of
organobentonite with longer alkyl chains leads to
gradual desorption of surfactant and/or fragmenta-
tion of the alkylammonium cation itself (Xie et al.,
2001).
The cation exchange capacity (CEC) of bento-
nite, using methylene blue, barium chloride and
ammonium acetate methods, was found to be
9 8 0 m m o l k g 1 , 7 9 6 . 1 m e q k g 1 a n d
565.4 meq kg1, respectively.
The ratio of C/N for modified-bentonite, obtained
from elemental analysis results, was 15.32; the
calculated value of the C/N ratio for HDTMA was

FIG. 5. Thermogravimetric (TG) and differential thermogravimetric (DTG) curves of (a) natural bentonite,
(b) HDTMA-Br and (c) HDTMA-bentonite.
38 G. A. Ikhtiyarova et al.

16.29 and the percentage of HDTMA onto

bentonite was 28.48%. These results confirm that
the modification of natural bentonite with HDTMA-
Br was achieved.
The alkylammonium cations concentration ca per
gram of the inorganic part of the organoclay can be
calculated by using equation 1
cm
ca ¼ ð1Þ
1  ðcm  MMÞ

where cm is the concentration of HDTMA in the

organoclay (in mol g1), MM is the molecular mass
of the alkylammonium cation (284.55 g mol1). It
was found that ca = 1.40 mmol g1 for HDTMA- FIG. 6. pH effect for the adsorption of RB19 onto
bentonite; therefore the values of ca related to CEC natural bentonite and HDTMA-bentonite at 20ºC.
by using methylene blue, barium chloride and
ammonium acetate methods are 1.43, 1.76 and
2.48 CEC, respectively (Majdan et al., 2009). values and so the adsorption decreases. The results
The BET surface areas of natural bentonite and indicate that the adsorption of RB19 onto HDTMA-
HDTMA-bentonite are 67.49 and 19.28 m2 g1, bentonite is greater than natural bentonite. The
respectively. Since the interparticle pores of variation in the removal of RB19 with respect to pH
smectite are covered and the interlamellar spaces can be explained by considering the surface charge
are blocked, leading to the inhibition of the passage of the adsorbent. The higher adsorption capacity of
of N2 molecules, the BET surface area has the dye onto HDTMA-bentonite at low pH values
decreased by more than three times with the may be due to neutralization of the negative charge
modification. at its surface as the SO 3 anion, which increases
the protonation and solubility of dye and, in other
words, increases the electrostatic attraction between
Effect of pH
the negatively charged SO 3 anion and the
One of the important parameters controlling the positively charged adsorption site. The reason for
adsorption process is pH and its influence on the the high adsorption capacity at low pH values is
amount of RB19 adsorption onto natural bentonite due to the strong electrostatic interaction between
and HDTMA-bentonite was studied in the pH range the cationic surfactant head groups (N+(CH3)3)
1.59.5. It was found that the amount of RB19 and dye anions.
adsorption decreases with an increase in pH, as can
be seen from Fig. 6. The optimum pH was then
determined as 1.5 and used throughout all the
adsorption experiments.
When the initial pH of the dye solution was
increased from 1.5 to 9.5, the amount of adsorbed
dye decreased from 120.7 to 16.43 mg g1 for
natural bentonite and from 350.6 to 168.3 mg g1
for HDTMA-bentonite. The reason for a high
adsorption at lower pH values is that the adsorbent
surface increases the interaction between the
positively charged clay surface and the negatively
charged dye molecules. A low adsorption at greater
pH values may be due to the abundance of OH
ions and because of ionic repulsion between the
negatively charged surface and the anionic dye
molecules. There are also no exchangeable anions FIG. 7. Effect of contact time for the adsorption of
on the outer surface of the adsorbent at higher pH RB19 onto natural bentonite.
 Characterization and adsorption behaviour of bentonite 39

Effect of contact time

The influence of contact time on RB19 removal

by natural bentonite and HDTMA-bentonite is
shown in Fig. 7. It can be seen that the rate of
removal of RB19 by adsorption was rapid initially
and then slowed down gradually until it attained an
equilibrium beyond which there was no significant
increase in the rate of removal. The maximum
adsorption of RB19 onto natural bentonite and
HDTMA-bentonite was observed at 50 min. After
this time, the adsorption rate was slow, leading to a
single, smooth and continual saturation curve and at
FIG. 9. Pseudo-second-order kinetic plots for the
longer times almost no adsorption took place. 50
adsorption of RB19 onto HDTMA-bentonite at various
min was therefore fixed as the equilibrium contact temperatures.
time.
Adsorption kinetics and isotherm
Effect of temperature
The pseudo-second-order kinetic model equation
The equilibrium adsorption capacity of HDTMA- (equation 2) (Ho & McKay, 1998; Azizian, 2004)
bentonite for RB19 was found to decrease with has been applied to the experimental data to obtain
i n c r e a s i n g t e mp e r a t u re , d e c r e a s i n g f r o m information about the adsorption mechanism.
344.9 mg g1 at 20ºC to 330.6 mg g1 at 40ºC
t 1 1
(Fig. 8), indicating that the dye adsorption on the ¼ þ t ð2Þ
qt kq2max qmax
adsorbent surface was favoured at lower tempera-
tures. This may be due to a tendency for RB19 ions
to escape from the solid phase to the bulk phase where qt is the amount of dye adsorbed (mg g1) at
with an increase in the temperature of the solution various times t, qmax is the maximum adsorption
and due to a weakening in van der Waals forces of capacity (mg g1) and k is the rate constant of
attraction between RB19 and HDTMA-bentonite pseudo-second-order adsorption (g mg1 min1).
(Tsai et al., 2004; Singh, 1998). This effect The straight line plots of t/qt against t for HDTMA-
suggests that an explanation of the adsorption bentonite (Fig. 9) have been drawn to obtain rate
mechanism associated with the removal of RB19 parameters. The k, qmax and correlation coefficient,
onto HDTMA-bentonite involves a physical r2 values of the dye under different conditions were
exothermic process. calculated from these plots and are given in

FIG. 8. The adsorption of RB19 onto HDTMA- FIG. 10. Langmuir adsorption isotherm plots of RB19
bentonite at various temperatures. onto HDTMA-bentonite at various temperatures.
40 G. A. Ikhtiyarova et al.

TABLE 1. Pseudo-second-order kinetic parameters for the adsorption of RB19

onto HDTMA-bentonite at various temperatures.

—————— T (ºC) ——————

20 30 40

k2 (g mg1 min1) 1.066102 1.246102 1.736102

q2 (mg g1) 344.9 340.4 330.6
r22 0.999 0.999 0.999

Table 1. As can be seen, the correlation coefficients
(r2) for HDTMA-bentonite are 0.999. These results
emphasize that the adsorption system follows the
pseudo-second-order kinetic model and the pseudo-
second-order rate constants are affected by an
increase in temperature.
The pseudo-second-order rate constants for RB19
onto HDTMA-bentonite systems indicate a steady
increase with temperature. The values of rate
constants were found to increase from 1.066102
to 1.73610 2 g mg 1 min 1 for HDTMA-
bentonite with an increase in the solution
temperatures from 20ºC to 40ºC (Table 1).
The analysis of equilibrium data for the
adsorption of RB19 onto HDTMA-bentonite has
been tested by the linear form (equation 3) of the
Langmuir (1918) isotherm equation.
Ce 1 Ce
¼ þ ð3Þ
qe qmax KL qmax
where qe is the equilibrium dye concentration on
the adsorbent (mg g1), Ce is the equilibrium dye
concentration in the solution (mg dm3), qmax is the
monolayer capacity of the adsorbent (mg g1) and
KL is the Langmuir constant (dm3 mg1). A plot of
Ce/qe vs. Ce gives a straight line of slope, 1/qmax,
and the intercept, 1/(q max K) (Fig. 10). The
Langmuir adsorption is the monolayer adsorption
and the Langmuir equation is applicable to
homogeneous adsorption, where the adsorption of
each adsorbate molecule onto the surface is equal to
the adsorption activation energy.
The values of the Langmuir constant (KL), the
monolayer capacity of adsorbent (qmax) and the
correlation coefficients (r2L) are listed in Table 2. As
can be seen from Table 2, the correlation coeffi-
cients (r2L), for HDTMA-bentonite are between
0.993 and 0.997. These results indicate that the
adsorption system fits well to the Langmuir
isotherm model.
The favourability of the adsorption process was
confirmed by using a basic method, which suggests
that the linear, favourable or unfavourable, the
nature of the isotherm is dependent on the values
obtained for the separation factor (RL) as unity,
between 01 or zero, respectively. In this manner,
the Langmuir constant, KL , can be used to
determine the applicability of the adsorbent for
the removal of RB19 by using RL (dimensionless)
following equation 4 (Weber & Chakravorti, 1974;
Hall et al., 1966).
1
RL ¼ ð4Þ
1 þ KL C0
where Co is the highest initial RB19 concentration
(mg dm3). The calculated values of RL were found

TABLE 2. Langmuir adsorption isotherm constants for the adsorption of RB19 onto
HDTMA-bentonite at various temperatures.

——————— T (ºC) ———————

20 30 40

qmax (mg g1) 502.0 496.5 468.5

KL (dm3 mg1) 2.946102 2.436102 2.256102
r2L 0.997 0.995 0.993
RL 5.836102 6.976102 7.466102
 TABLE 3. Adsorption results of RB19 from the literature by various adsorbents and operating conditions.

—————————————— Operating conditions ——————————————

Adsorbent material Adsorption pH T Initial concentration Amount of Reference
capacity (mg g1) (ºC) range (mg dm3) adsorbent (g dm3)

Fly ash 135.7 6.0 20 100500 6.0 Dizge et al., 2008

Zinc oxide powder (Z300) 89.3 4.0 25 50500 0.2 Ada et al., 2009
Zinc oxide powder (Z075) 38.9 4.0 25 50500 0.2 Ada et al., 2009
Waste metal hydroxide sludge 275.0 4.0 25  1.0 Santos et al., 2008
Green algae (Scenedesmus quadricauda) heat 95.2 2.0 30 25200 0.513 Ergene et al., 2009
inactivated immobilized in alginate gel beads
(IHISq)
Green algae (Scenedesmus quadricauda) heat 68.0 2.0 30 25200 0.534 Ergene et al., 2009
active immobilized in alginate gel beads (IASq)
Basic oxygen furnace slag (BOF slag) 60.0 2.0 25 25500 5 Xue et al., 2009
Porous MgO powder 166.7 8.0 25 50300 2 Moussavi &
Mahmoudi, 2009
Chitosan/oil palm ash composite beads 416.7 6.0 30 50500 2 Hasan et al., 2008
DAH-bentonite 134.6 5.0 20 62.6219 0.5 Gök et al., 2010
DTMA-bentonite 206.6 1.5 20 125282 0.6 Özcan et al., 2007
HDTMA-bentonite 502.0 1.5 20 200550 0.5 This study
Characterization and adsorption behaviour of bentonite
41
42 G. A. Ikhtiyarova et al.
from this equation to be between 5.836102 and
7.466102 at various temperatures and are given in
Table 2. The results indicates that adsorption of
RB19 ions onto HDTMA-bentonite is favourable.
In this study, the maximum adsorption capacity
of HDTMA-bentonite obtained for RB19 was
502.0 mg g 1 from the Langmuir adsorption
isotherm model. As can be seen from Table 3, the
maximum adsorption capacity of HDTMA-bento-
nite was found to be higher than that of many
corresponding adsorbents reported in the literature.
Thermodynamic parameters
The Langmuir constant KL can be used for
calculating thermodynamic parameters including the
changes in free energy (DGº), enthalpy (DHº) and
entropy (DSº), which are associated with the
adsorption process, on the basis of the following
equations:
DG0 ¼ RT ln KL ð5Þ
DS 0 DH 0
ln KL ¼  ð6Þ
R RT
The plot of lnKL as a function of 1/T yields a
straight line from which DHº and DSº were
calculated from the slope and intercept, respec-
tively. The DGo values are 23.93 kJ mol1 at
2 0 º C , 2 4 . 2 7 k J m o l 1 a t 3 0 º C a n d
24.87 kJ mol1 at 40ºC, which indicates the
nature of the spontaneous adsorption. The negative
value of DHº (10.11 kJ mol1) indicates that the
adsorption is exothermic and the value of DHº
implies that adsorption is also physical in nature
involving weak forces of attraction. The positive
value of DSº (+46.99 J mol1 K1) corresponds to
an increase in the degree of freedom of the
adsorbed species.
CONCLUSION
The present study clearly demonstrates that
hexadecyltrimethylammonium (HDTMA)-bromide-
modified bentonite is an effective adsorbent for the
removal of RB19 from aqueous solution. The XRD
results revealed randomly lateral-monolayer
arrangements of the intercalated alkylammonium
cation into bentonite. The basal space of adsorbent
increases from 14.87 to 19.03 Å with modification.
The SEM photomicrographs clearly indicate that
natural bentonite, after modification, loses its
foliated structure and gains more rough surface.
TGA and DTG results confirm the modification of
bentonite with surfactant cations. Since the pores of
natural bentonite experience coverage with modifi-
cation the BET surface area is decreased.
After the characterization, the removal of a
textile dye, Reactive Blue 19 (RB19), onto the
natural bentonite and HDTMA-bentonite was
investigated. The adsorption was found to be
strongly dependent on pH, contact time and
temperature. The maximum adsorption capacity
for the removal of RB19 obtained from the
Langmuir adsorption isotherm model was found to
be 502.0 mg g1 at pH 1.5 and 20ºC. This is the
highest value recorded when compared with the
literature values. It may be concluded that
HDTMA-bentonite acts as a respective adsorbent
for the removal of RB19 in aqueous solutions due
to its high adsorption capacity. The adsorption of
RB19 onto HDTMA-bentonite was exothermic in
nature with the dye removal capacity decreasing
with increasing temperature due to increasing
mobility of the dye molecules. The adsorption of
RB19 onto HDTMA-bentonite follows the pseudo-
second-order kinetic model with high correlation
coefficients. The thermodynamic parameters for
RB19 adsorption obtained from the Langmuir
constant (KL) indicate a physical, feasible, sponta-
neous and exothermic adsorption.
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