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Colloids and Surfaces A: Physicochem. Eng.

Aspects 266 (2005) 7381

Adsorption of Acid Blue 193 from aqueous solutions

onto BTMA-bentonite
A. Safa Ozcan , Bilge Erdem, Adnan Ozcan
Anadolu University, Faculty of Science, Department of Chemistry, Yunusemre Campus, 26470 Eskisehir, Turkey

Received 11 January 2005; received in revised form 31 May 2005; accepted 1 June 2005


The adsorption of Acid Blue 193 (AB193) onto benzyltrimethylammonium (BTMA)-bentonite was investigated in aqueous solution in
a batch system with respect to contact time, pH and temperature. The surface modification of BTMA-bentonite was examined using the
FTIR technique. The pseudo-first-order, pseudo-second-order kinetic models and the intraparticle diffusion model were used to describe the
kinetic data and the rate constants were evaluated. The experimental data fitted very well the pseudo-second-order kinetic model and also
followed the intraparticle diffusion model up to 60 min, whereas diffusion is not only the rate controlling step. The Langmuir, Freundlich
and DubininRadushkevich (DR) adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were
also determined. The Langmuir, Freundlich and DR models agree with experimental data well. The change of free energy, enthalpy and
entropy of adsorption were also evaluated for the adsorption of AB193 onto BTMA-bentonite. The results show that BTMA-bentonite could
be employed as low-cost material for the removal of acid dyes from effluents.
2005 Elsevier B.V. All rights reserved.

Keywords: Bentonite; Adsorption; Acid dye; Surfactant; Kinetics

1. Introduction biodegradable nature of dyes, which are stable to light and

oxidation [13].
Colored dyes are important water pollutants which are Adsorption is one of the effective methods to remove col-
generally present in the effluents of the textile and other ored textile contaminants from wastewaters. Adsorption phe-
industries. The high level of production and extensive use of nomenon in solution systems plays a vital role in many areas
dyes generates colored wastewater which produces toxico- of practical environmental technology, which are mainly in
logical and technical problems and environmental pollution. water and wastewater treatment due to several advantages
Some dyes, for instance, are reported to cause allergy, der- such as high efficiency, simple operation and easy recov-
matitis, skin irritation, cancer and mutation in human. Thus, ery/reuse of adsorbent [46]. Even though the most promising
the removal of color dyes from wastewater before they are adsorbent for adsorption is activated carbon, which has a high
contacted with unpolluted natural water bodies is impor- surface area and a high adsorption capacity, it is very expen-
tant. Although several traditional chemical and biological sive, has high operation costs and there is a need for regen-
processes exist for dye removal, the application of these eration after each adsorption cycle [79]. Therefore, there is
techniques has been restricted due to the essentially non- a growing need to find low cost and efficient, locally avail-
able materials for the removal of dyes. Some clays such as
Corresponding author. Tel.: +90 222 3350580/5781;
sepiolite [10], kaolinite [11], montmorillonite [12], smectite
fax: +90 222 3204910.
[13], bentonite [3,14] and alunite [15] have been investigated
E-mail addresses: (A.S. Ozcan), for this purpose. These kinds of clays have a variety of sur- (B. Erdem), (A. Ozcan). face and structural properties, high chemical stability, high

0927-7757/$ see front matter 2005 Elsevier B.V. All rights reserved.
74 A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381

specific surface area and high adsorption capacity and hence

they can be used to remove dye from effluents.
The water-soluble anionic dyes are used to dye fabrics,
such as wool, nylon and silk. Because of the weak interactions
between the negatively charged surface in clays and anionic
dyes, a few studies on the adsorption of acid dyes have been
carried out using bentonite as an adsorbent [3,1618], but
none of them has investigated adsorption of Acid Blue 193
Fig. 1. Chemical structure of AB193.
(AB193) dye onto BTMA-bentonite. In addition, this kind
of clay is mainly used as an emulsifying agent for aspaltic
and resinous substances, as an adhesive agent in horticultural
sprays and insecticides, in concrete mixtures, and as a plasti- 2. Materials and methods
cizer in ceramic materials. It is also used in refining oils and
fats, drilling mud, foundry sands, in some detergents, cos- 2.1. Materials
metics, pharmaceuticals, thickeners and extenders for paints,
coating and filling of paper [19,20]. Bentonite is natural A commercial textile dye AB193 (Isolan Dark Blue 2-
clay which contains montmorillonite. The inner layer is con- SGL) was obtained from Dystar, Turkey, and used without
sisted of an octahedral sheet situated between two tetrahedral further purification. The chemical structure of AB193 is
sheets. Substitutions within the lattice structure of trivalent depicted in Fig. 1. Bentonite was provided from Canakkale,
aluminum for quadrivalent silicon in the tetrahedral sheet and Turkey. It was crushed, ground, sieved through a 63-m sieve
of ions of lower valence, especially magnesium, for trivalent and dried at 110 C in an oven for 2 h prior to use. The deter-
aluminum in the octahedral sheet result in unbalanced charges mined cation exchange capacity (CEC) and the surface area
in the structural units of clays. The above factors generally of the natural bentonite by the methylene blue method [24]
cause a good adsorbent for the removal of dye in aqueous were 980 mmol kg1 and 767 m2 g1 , respectively.
solutions [3,21].
The surface properties of bentonite may be greatly mod-
2.2. Material characterization
ified with a surfactant by simple ion-exchange reactions
to lead van der Waals interaction between organic surfac-
The chemical analysis of natural bentonite was determined
tant cations and adsorbate. The modification of clay surface
by using an energy dispersive X-ray spectrometer (EDX-
with surfactant is called as organoclay to cause to trans-
LINK ISIS 300) attached to a scanning electron microscope
form organophobic to strongly organophilic and therefore the
(SEM-Cam Scan S4).
adsorption capacity increases [22]. This kind of surfactant-
FTIR spectra for bentonite and BTMA-bentonite were
modified organobentonite has been used extensively for a
recorded (KBr) on a Jasco FT/IR-300E Model Fourier trans-
wide variety of environmental applications [23].
form infrared spectrometer to confirm the surface modifica-
The characteristics of the adsorption behavior are usu-
ally understood by means of both equilibrium isotherm
and adsorption kinetics. The adsorption isotherm is also an
inevitable tool for the theoretical evaluation and interpre- 2.3. Preparation of BTMA-bentonite
tation of thermodynamic parameters including changes in
Gibbs free energy, entropy and enthalpy. In this type of study, Bentonite was firstly washed with deionized water by sev-
the construction of an adsorption isotherm plays an important eral times and then the Na+ -exchanged form of clay was
role in understanding the adsorption mechanism. For adsorp- prepared by stirring samples for 24 h with 1 N NaCl. This
tion kinetics, temporal variations of the amount of adsorption was followed by several washings with distilled water and
are measured and thus the obtained experimental data are filtered to remove the excess NaCl and other exchangeable
used to develop a proper kinetic model [5,6]. cations from the clay. The clay was then resuspended and
The present paper is to investigate the possibility of filtered until a negative chloride test was obtained with 0.1 M
BTMA-bentonite as an adsorbent for removal of an anionic AgNO3 .
acid dye, which is, namely Acid Blue 193, from aqueous solu- Twenty grams of the Na-saturated clay was dispensed
tion by adsorption method. The adsorption capacity of AB193 in 0.5 dm3 of distilled water. Benzyltrimethylammonium
onto BTMA-bentonite was carried out using various kinetic (BTMA) chloride was used as a surfactant. BTMA-bentonite
models. The experimental data were fitted into Langmuir, was prepared by adding quantities of the respective chloride
Freundlich and DubininRadushkevich (DR) equations to salts equal to twice the cation exchange capacity of the ben-
determine which isotherm gives the best correlation to experi- tonite and stirring for 24 h. The clay was then washed with
mental data. The calculated thermodynamic parameters from distilled water until free of salts and a negative chloride test
the Langmuir isotherm constant were also used to explain the had been obtained with 0.1 M AgNO3 and was used for the
nature of adsorption. adsorption studies [25].
A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381 75

The elemental analysis (Vario EL III Elemental Analyzer,

Hanau, Germany) of BTMA-bentonite was carried out to
determine C/N ratio in BTMA-bentonite.

2.4. Adsorption experiments

The pH experiments were carried out by 50 ml of a

250 mg dm3 dye solutions with 0.01 g of BTMA-bentonite
and the pH was carefully adjusted between 1 and 11 with
adding a small amount of dilute HCl or NaOH solution
using a pH meter (Fisher Accumet AB15). The dye solutions
were stirred using a mechanical magnetic stirrer in a 100 ml
erlenmeyer sealed with parafilm to avoid evaporation. The
optimum pH was then determined as 1.5 and used throughout
all adsorption experiments, which were conducted at various
time intervals, the initial concentrations (100250 mg dm3 )
Fig. 2. FTIR spectra of: (a) natural bentonite () and (b) BTMA-bentonite
(- - -).
and temperatures (20, 30 and 40 C), to determine the adsorp-
tion equilibrium time and the maximum removal of dye. The
The ratio of C/N for BTMA-bentonite from elemental
solutions were filtered and then subjected to quantitative anal-
analysis results is 8.95 and the calculated value of C/N ratio
yses. The equilibrium concentrations of each solution were
for BTMA is 8.57 and the percentage of BTMA onto clay is
measured by spectrophotometer (Shimadzu UV-2101PC) at
11.13. These results confirm that the intercalation of BTMA
the max value, which is 609 nm for AB193. The amount of
molecules between the bentonite layers occurs, and these
the dye adsorbed onto BTMA-bentonite surface was deter-
results are also consistent with FTIR results.
mined by the difference between the initial and remaining
concentrations of dye solution.
The adsorption of AB193 onto BTMA-bentonite was also 3.2. FTIR analysis
evaluated at constant temperatures of 20, 30 and 40 C for
the adsorption isotherms. FTIR spectra of natural bentonite and BTMA-bentonite
are illustrated in Fig. 2. There is a group of absorption
peaks between 3427 and 3626 cm1 , which is due to stretch-
3. Results and discussion ing band of the OH groups and bending bands at 914 and
890 cm1 . The band at 1637 cm1 also corresponds to the
3.1. Chemical composition of bentonite OH deformation of water to observe natural bentonite and
BTMA-bentonite, but the peak intensity of BTMA-bentonite
The chemical composition of bentonite obtained by using is lower than natural bentonite. This may be acceptable evi-
EDX analysis, given in Table 1, indicates the presence of dence for the surface modification occurring on bentonite.
silica and alumina as major constituents along with traces of For the band at 3037 cm1 , which is characteristic of aro-
sodium, potassium, iron, magnesium, calcium and titanium matic C H bonds of BTMA (surfactant) and is generally
oxides in the form of impurities. XRD results combined with rather low intensity and occurs just to the left of a nor-
EDX analysis show that most of the aluminum is in the form mal saturated C H band, and the bands between 1450 and
of bentonite. XRD also indicated the presence of free quartz 1600 cm1 , characteristic peaks are assigned to the stretch-
in bentonite. It is, thus, expected that the adsorbate species ing vibrations of aromatic ring double bond. In addition,
will be removed mainly by SiO2 and Al2 O3 . the bands at 690900 cm1 range are due to C H out-of-
plane bending of aromatic surfactant. These bands were only
Table 1
observed for BTMA-bentonite and these could be an accept-
Chemical composition of bentonite able evidence for the modification.
Constituents wt%
The bands at 2854, 2927 and 2962 cm1 were only
observed for BTMA-bentonite. They can be assigned to
SiO2 70.75
Al2 O3 16.18
the symmetric and asymmetric stretching vibrations of the
K2 O 2.12 methyl and methylene groups and their bending vibrations are
CaO 1.62 between 1380 and 1475 cm1 [26] supporting the intercala-
MgO 1.25 tion of surfactant (BTMA) molecules between the silica lay-
Fe2 O3 0.70 ers, but these stretching and bending bands are not observed
TiO2 0.18
Na2 O 0.11
in the natural bentonite. The stretching band of the SiO was
observed at 1041 cm1 . The bands at 519 and 467 cm1 for
Loss of ignition 6.63
natural bentonite and BTMA-bentonite were from SiOAl
76 A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381

Fig. 3. pH effect for the adsorption of AB193 onto BTMA-bentonite at

20 C.

(where Al is an octahedral cation) and bending vibrations,


3.3. Effect of pH

Fig. 3 indicates the effect of pH on the removal of dye

(AB193) onto BTMA-bentonite from aqueous solution. It
was observed that the adsorption is highly dependent on
pH of the solution which affects the surface charge of the
adsorbent and the degree of ionization and speciation of
adsorbate. At lower pH, more protons will be available,
thereby increasing electrostatic attractions between nega-
tively charged dye anions and positively charged adsorption
sites and causing an increase in dye adsorption [3]. The high
adsorption capacity is due to the strong electrostatic inter-
action between the N+ (CH3 )3 of BTMA-bentonite and dye
As can be seen (Fig. 3), the maximum AB193 removal
was observed at acidic pH 1.5. When the pH of the solu-
tion is increased, the positive charge on the oxide or solution
interface decreases and the adsorbent surface appears nega-
tively charged. On the contrary, a lower adsorption at higher
pH values may be due to the abundance of OH ions and Fig. 4. Effect of contact time for the adsorption of AB193 onto BTMA-
because of ionic repulsion between the negatively charged bentonite at various temperatures.
surface and the anionic dye molecules. There are also no
exchangeable anions on the outer surface of the adsorbent at 472.4 mg g1 at 40 C. These indicate that the initial dye con-
higher pH values and consequently the adsorption decreases centrations play an important role in the adsorption capacities
[27]. of AB193 on the BTMA-bentonite.
The effect of contact time on the amount of AB193,
3.4. Effect of initial dye concentration, contact time and adsorbed onto BTMA-bentonite at various temperatures
temperature (Fig. 4), was also investigated at the range of initial dye con-
centration of 100250 mg dm3 . When the equilibrium time
The influence of the initial concentrations of AB193 in the was increased, the amount of adsorption was not increased.
solutions on the rate of adsorption onto BTMA-bentonite was The rate of removal of AB193 onto BTMA-bentonite by
investigated between 100 and 250 mg dm3 at the initial pH adsorption was rapid initially and then slows down gradually
value of 1.5. As shown in Fig. 4, when the initial dye concen- until it attained an equilibrium beyond which there was no
trations were increased from 100 to 250 mg dm3 , the adsorp- significant increase in the rate of removal. Maximum adsorp-
tion capacity of dye increased from 252.8 to 505.3 mg g1 at tion capacity of AB193 onto BTMA-bentonite was observed
20 C, from 234.7 to 480.4 mg g1 at 30 C and from 209.5 to at 60 min; it can be said that beyond this, there is almost no
A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381 77

further increase in the adsorption and it is thus fixed as the where q1 and qt are the amounts of the dye adsorbed at equi-
equilibrium contact time. librium and at time t (mg g1 ) and k1 is the pseudo-first-order
The equilibrium adsorption capacity of AB193 onto rate constant (min1 ), applied to the adsorption of AB193.
BTMA-bentonite was also affected by temperature and Values of k1 calculated from the slope of the plots of 1/qt
decreased with increasing temperature from 20 to 40 C versus 1/t are shown in Table 2 (figure not shown). It was
which indicates that the adsorption of AB193 onto BTMA- found that the correlation coefficients for the pseudo-first-
modified adsorbent surface was favored at lower temperatures order model are lower than the pseudo-second-order model.
and it is controlled by an exothermic process. This is partly This indicates that the adsorption of AB193 onto BTMA-
due to a weakening of the attractive forces [28,29] between bentonite does not follow pseudo-first-order kinetics.
AB193 and BTMA-bentonite. Based on the above results, it The pseudo-second-order kinetic model [30] is expressed
implies that physical adsorption mechanism may play a vital as:
role in this system. Before and after equilibrium time, the
adsorption capacity shows different trends at various temper-
t 1 1
atures. In general, below the equilibrium time, an increase = + t, (2)
in the temperature leads to an increase in dye adsorption qt k2 q 2
2 q 2
rate, which shows a kinetically controlling process. After the
equilibrium attained, the uptake decreases with increasing
temperature indicating that the adsorption of AB193 onto where q2 is the maximum adsorption capacity (mg g1 )
BTMA-bentonite from aqueous solution is controlled by an for the pseudo-second-order adsorption and k2 is the equi-
exothermic process. librium rate constant of pseudo-second-order adsorption
(g mg1 min1 ). Values of k2 and q2 were calculated from
the plot of t/qt against t (Fig. 5). All of kinetic data of AB193
under different conditions were calculated from plots and
3.5. Kinetics of adsorption
are given in Table 2. The correlation coefficients for the
second-order kinetic plots at all the studied concentrations
The kinetics of adsorption is one of the most important
were generally above 0.999 (Table 2) and the calculated q2
characteristics in defining the efficiency of adsorption. Vari-
values also agree with experimental q2 values. These results
ous kinetic models have been proposed by different research
imply that the adsorption system studied obeys to the second-
groups where the adsorption has been treated as a pseudo-
order-kinetic model, a similar phenomenon which we have
first-order [30], a pseudo-second-order [30] and intraparticle
observed in the adsorption of acid dyes by acid-activated ben-
diffusion [31]. The pseudo-first-order kinetic model equation
tonite [14] and sepiolite [10].
The pseudo-first-order and pseudo-second-order kinetic
models cannot identify the diffusion mechanism and the
1 k1 1 kinetic results were then analyzed by using the intraparti-
= + , (1)
qt q1 t q1 cle diffusion model. The intraparticle diffusion equation [31]

Table 2
Kinetic parameters for the adsorption of AB193 at various temperatures
t ( C) Co (mg dm3 ) k1 (min1 ) q1 (mg g1 ) r12 k2 (104 ) q2 (mg g1 ) r22 kp (mg g1 min1/2 ) C (mg g1 ) rp2
(g mg1 min1 )
20 100 2.024 257.7 0.936 12.85 260.7 0.999 7.681 195.72 0.945
150 3.425 353.6 0.960 8.702 352.6 0.999 16.23 222.51 0.948
175 3.170 394.2 0.915 7.090 398.3 0.999 16.74 257.45 0.914
200 3.540 438.6 0.955 6.829 437.4 0.999 20.28 273.57 0.921
225 3.300 488.5 0.926 6.334 478.5 0.992 21.51 316.99 0.826
250 3.003 515.5 0.918 5.911 518.9 0.999 19.09 355.49 0.819
30 100 2.573 237.6 0.990 16.22 237.6 0.999 7.965 171.81 0.869
150 2.585 330.7 0.895 10.18 333.6 0.999 10.69 240.52 0.779
175 1.751 364.4 0.804 8.837 377.6 0.999 7.987 294.52 0.795
200 3.016 422.8 0.924 7.500 423.3 0.999 15.54 292.29 0.777
225 2.631 469.3 0.860 6.986 473.4 0.999 14.84 342.30 0.722
250 2.997 495.1 0.977 6.905 494.5 0.999 19.21 336.21 0.923
40 100 1.724 211.6 0.666 17.32 216.3 0.999 5.714 165.73 0.751
150 2.678 316.9 0.961 11.82 316.7 0.999 11.10 225.55 0.836
175 2.643 360.9 0.882 9.551 363.0 0.999 12.33 258.20 0.793
200 4.922 435.5 0.856 8.339 415.1 0.999 21.72 250.91 0.686
225 2.803 460.4 0.964 8.326 458.8 0.999 17.40 318.90 0.884
250 3.002 487.1 0.938 7.229 485.8 0.999 20.08 324.82 0.899
78 A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381

els may control the rate of adsorption, all of which may be

operating simultaneously. The slope of linear portion from
the figure can be used to derive values for the rate parameter,
kp , for the intraparticle diffusion, given in Table 2. The cor-
relation coefficients (rp2 ) for the intraparticle diffusion model
are also lower than the pseudo-second-order model but this
model indicates that the adsorption of AB193 onto BTMA-
bentonite may be followed by an intraparticle diffusion model
up to 60 min. The values of intercept give an idea about the
boundary layer thickness such as the larger the intercept, the
greater is the boundary layer effect.
The pseudo-second-order rate constants for AB193 onto
BTMA-bentonite indicate a steady increase with tempera-
ture. The values of rate constants were found to increase at
all the studied concentrations for BTMA-bentonite with an
increase in the solution temperatures from 20 to 40 C. It may
be concluded that the adsorption of AB193 onto BTMA-
bentonite follows a physisorption mechanism, increasing
temperature generally increases the rate of approach to equi-
librium, but decreases the equilibrium adsorption capacity

3.6. Adsorption isotherms

The equilibrium adsorption isotherm is one of the most

important data to understand the mechanism of the adsorp-
tion systems. Several isotherm equations are available
and three important isotherms are selected in this study,
which are, namely the Langmuir [34], Freundlich [35] and
DubininRadushkevich [36] isotherms.
The Langmuir adsorption isotherm assumes that adsorp-
tion takes place at specific homogenous sites within the adsor-
bent and has found successful application in many adsorption
processes of monolayer adsorption. The linear form of the
Langmuir isotherm equation is represented by the following
1 1 1 1
= + , (4)
qe qmax qmax KL Ce
where qe is the equilibrium dye concentration of the adsor-
Fig. 5. Pseudo-second-order kinetic plots for the adsorption of AB193 onto
BTMA-bentonite at various concentrations and temperatures.
bent (mol g1 ), Ce the equilibrium dye concentration in the
solution (mol dm3 ), qmax the monolayer adsorption capacity
of the adsorbent (mol g1 ) and KL is the Langmuir adsorp-
can be written by following:
tion constant (dm3 mol1 ) and related to the free energy of
qt = kp t 1/2 + C, (3) adsorption. The plots of 1/qe versus 1/Ce for the adsorption
of AB193 onto BTMA-bentonite (Fig. 6) give a straight line
where C is the intercept and kp is the intraparticle diffusion of slope qmax1 KL and intercept qmax
rate constant (mg g1 min1/2 ). According to this model, the The Freundlich isotherm is an empirical equation
plot of uptake, qt , versus the square root of time, t1/2 (fig- employed to describe heterogeneous systems. A linear form
ure not shown), should be linear if intraparticle diffusion is of the Freundlich equation is
involved in the adsorption process and if these lines pass
through the origin, then intraparticle diffusion is the rate con- ln qe = ln KF + ln Ce , (5)
trolling step [7,32,33]. When the plots do not pass through n
the origin, this is indicative of some degree of boundary layer where KF (dm3 g1 ) and n are Freundlich adsorption isotherm
control and this further shows that the intraparticle diffusion constants, being indicative of the extent of the adsorption and
is not the only rate-limiting step, but also other kinetic mod- the degree of nonlinearity between solution concentration and
A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381 79

Fig. 6. Langmuir plots for the adsorption of AB193 onto BTMA-bentonite Fig. 8. DubininRadushkevich plots for the adsorption of AB193 onto
at various temperatures. BTMA-bentonite at various temperatures.

where is a constant related to the mean free energy of

adsorption per mole of the adsorbate (mol2 J2 ), qm the the-
oretical saturation capacity and is the Polanyi potential,
which is equal to RT ln(1 + C1e ), where R (J mol1 K1 ) is
the gas constant and T (K) is the absolute temperature. Hence,
by plotting ln qe versus 2 , it is possible to obtain the value of
qm (mol g1 ) from the intercept and the value of from the
slope. Fig. 8 indicates the DR isotherm for AB193 adsorp-
tion onto BTMA-bentonite.
The constant gives an idea about the mean free energy E
(kJ mol1 ) of adsorption per molecule of the adsorbate when
it is transferred to the surface of the solid from infinity in the
solution and can be calculated using the relationship [3840]:
E= (7)
Fig. 7. Freundlich plots for the adsorption of AB193 onto BTMA-bentonite (2)1/2
at various temperatures.
This parameter gives information whether adsorption mech-
adsorption, respectively. The plots of ln qe versus ln Ce for the anism is ion-exchange or physical adsorption. If the mag-
adsorption of AB193 onto BTMA-bentonite (Fig. 7) were nitude of E is between 8 and 16 kJ mol1 , the adsorption
employed to generate the intercept value of KF and the slope process follows by ion-exchange [41], while for the values of
of 1/n. E < 8 kJ mol1 , the adsorption process is of a physical nature
The DR isotherm is more general than the Langmuir [42]. The numerical value of adsorption of the mean free
isotherm because it does not assume a homogeneous surface energies between 8.975 and 8.177 kJ mol1 corresponds to
or constant adsorption potential. It was applied to distinguish a boundary of a physisorption and the predominance of van
between the physical and chemical adsorptions of dye [37]. der Waals forces.
The linear form of DR isotherm equation [36] is The Langmuir, Freundlich and DR parameters for the
adsorption of AB193 are listed in Table 3. It is evident from
ln qe = ln qm 2 (6) these data that the surface of BTMA-bentonite is made up

Table 3
Adsorption isotherm constants for the adsorption of AB193 onto BTMA-bentonite
t ( C) Langmuir Freundlich DubininRadushkevich (DR)

qmax (103 ) KL (dm3 mol1 ) rL2 RL KF (dm3 g1 ) n rF2 qm (102 ) (103 ) rD

R E (kJ mol1 )
(mol g1 ) (mol g1 ) (mol2 kJ2 )
20 2.228 3112.21 0.994 0.348 0.173 1.598 0.999 1.223 6.208 0.998 8.975
30 2.693 2060.37 0.996 0.447 0.298 1.431 0.994 1.566 6.510 0.950 8.764
40 6.039 656.62 0.997 0.717 0.974 1.177 0.990 2.774 7.478 0.993 8.177
80 A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381

of homogeneous and heterogeneous adsorption patches. In

other words, all of isotherm models fit very well when the r2
values are compared (Table 3). The Langmuir model correla-
tion coefficients are in a range of 0.9940.997, the Freundlich
model correlation coefficients are between 0.990 and 0.999
and the DR model correlation coefficients are in a range of
The effect of isotherm shape has been discussed [43] with
a view to predicting whether an adsorption system is favor-
able or unfavorable. The essential feature of the Langmuir
isotherm can be expressed by means of RL , a dimension-
less constant referred to as separation factor or equilibrium
parameter. RL is calculated using the following equation:
RL = , (8)
1 + K L Co
Fig. 9. Plot of ln KL vs. 1/T for estimation of thermodynamic parameters.
where KL is the Langmuir constant (dm3 mol1 )and Co is
the highest initial dye concentration (mol dm3 ). The values Go H o S o
ln KL = = + , (10)
of RL calculated from above equation are incorporated in RT RT R
Table 3. As the RL values lie between 0 and 1, the on-going The plot of ln KL as a function of 1/T (Fig. 9) yields a
adsorption process is favorable [43,44]. Further, the RL values straight line from which Ho and So were calculated from
for AB193 are between 0 and 1 and therefore, its adsorption the slope and intercept, respectively. The results are given in
is favorable. Table 4.
One of the Freundlich constants KF indicates the adsorp- Generally, the change of free energy for physisorption is
tion capacity of the adsorbent. The other Freundlich constant between 20 and 0 kJ mol1 , but chemisorption is a range
n is a measure of the deviation from linearity of the adsorp- of 80 to 400 kJ mol1 [46]. The overall standard free
tion. If a value for n is equal to unity, the adsorption is linear. energy change during the adsorption process was negative
If a value for n is below unity, this implies that adsorption for the experimental range of temperatures (see Table 4),
process is chemical, but if a value for n is above unity, adsorp- corresponding to a spontaneous physical process of AB193
tion is favorable, a physical process. The highest value of n adsorption and that the system does not gain energy from an
at equilibrium, 1.598 at 20 C, represents favorable adsorp- external source. When the temperature decreases from 40 to
tion at low temperature, and therefore this would seem to 20 C, the magnitude of standard free energy change shifts
suggest that physical, which is referred the adsorption bond to high negative value (from 16.89 to 19.60 kJ mol1 ) sug-
becomes weak [45] and conducted with van der Waals forces, gesting that the adsorption was rapid and more spontaneous
rather than chemical adsorption is dominant when it is used at low temperature [47].
for adsorbing AB193. The negative value of the standard enthalpy change
(59.06 kJ mol1 ) indicates that the adsorption is physical in
3.7. Thermodynamic parameters nature involving weak forces of attraction and is also exother-
mic, thereby demonstrating that the process is stable ener-
Because KL is equilibrium constant, its dependence with getically [48]. The negative standard entropy change (So )
temperature can be used to estimate thermodynamic param- value (133.56 J mol1 K1 ) corresponds to a decrease in
eters, such as change in the standard free energy (Go ), the degree of freedom of the adsorbed species.
enthalpy (Ho ) and entropy (So ) associated to the adsorp-
tion process and were determined by using following equa-
tions and represented in Table 4: 4. Conclusion

Go = RT ln KL , (9) From the foregoing experiments, the reasonable concludes

that BTMA-bentonite is an effective adsorbent for removing
Table 4 AB193 from aqueous solution, and it can be represented as
Thermodynamic parameters calculated from the Langmuir isotherm data for a suitable adsorbent and environmentally clean utilization of
the adsorption of AB193 onto BTMA-bentonite
t ( C) Go (kJ mol1 ) Ho (kJ mol1 ) So (J K1 mol1 ) The kinetics of adsorption of AB193 onto BTMA-
20 19.60 59.06 133.56 bentonite is studied on the basis of the pseudo-first-order,
30 19.23 pseudo-second-order and intraparticle kinetic models under
40 16.89
several different initial dye concentrations, temperatures
A.S. Ozcan et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 266 (2005) 7381 81

and pH. A pseudo-second-order and intraparticle diffusion [13] M. Ogawa, R. Kawai, K. Kuroda, J. Phys. Chem.-U.S. 100 (40)
kinetic models have been developed to predict the rate con- (1996) 16218.
[14] A.S. Ozcan, A. Ozcan, J. Colloid Interface Sci. 276 (1) (2004)
stants of adsorption and equilibrium adsorption capacities.
The high adsorption capacity of BTMA-bentonite in acidic [15] M. Ozacar, I.A. Sengil, J. Hazard. Mater. B98 (13) (2003) 211.
solutions (pH around 1.5) is due to the strong electrostatic [16] G. McKay, S.J. Allen, I.F. McConvey, Water Air Soil Pollut. 21
interactions between its adsorption site and dye anion. (1984) 127.
The adsorption isotherms of AB193 onto BTMA- [17] S. Kacha, Z. Derriche, S. Elmaleh, Water Environ. Res. 75 (1) (2003)
bentonite were analyzed according to Langmuir, Freundlich 15.
[18] K.R. Ramakrishna, T. Viraraghavan, Water Sci. Technol. 36 (23)
and DR models. All of three-isotherm models for AB193 (1997) 189.
adsorption were fitted very well with the experimental equi- [19] N. Rauf, S.S. Tahir, J. Chem. Thermodyn. 32 (5) (2000) 651.
librium data. The mechanism of the dyeBTMA-bentonite [20] W.A. Allo, H.H. Murray, Appl. Clay Sci. 25 (34) (2004) 237.
interaction is thus likely to be very complicated involving a [21] A. Ramesh, K.R. Mohan, K. Seshaiah, N.V. Choudary, Sep. Sci.
wide range of sites differing in a number of aspects including Technol. 37 (5) (2002) 1123.
[22] M. Akcay, J. Colloid Interface Sci. 280 (2) (2004) 299.
energy considerations. [23] Y.-H. Shen, Chemosphere 44 (5) (2001) 989.
The mean energy of adsorption is found from the DR [24] R.K. Taylor, J. Chem. Technol. Biotechnol. 35A (1985) 195.
isotherm. The small positive value of E (kJ mol1 ) indicates [25] Z. Li, R.S. Bowman, Water Res. 35 (16) (2001) 3771.
a low potential barrier and confirms the nature of physical [26] J. Madejova, Vib. Spectrosc. 31 (1) (2003) 1.
[27] Z. Wu, I.-S. Ahn, C.-H. Lee, J.-H. Kim, Y.G. Shul, K. Lee, Colloids
adsorption of AB193 onto BTMA-bentonite.
Surf. A: Physicochem. Eng. Aspect 240 (13) (2004) 157.
The enthalpy change (Ho ) for the adsorption process was [28] W.T. Tsai, C.W. Lai, K.J. Hsien, Chemosphere 55 (6) (2004) 829.
indicative of the exothermic nature of adsorption and a phys- [29] D. Singh, Adsorpt. Sci. Technol. 16 (8) (1998) 583.
ical adsorption. The Go values were negative; therefore, [30] Y.S. Ho, G. McKay, Chem. Eng. J. 70 (2) (1998) 115.
the adsorption was spontaneous and the negative value of [31] W.J. Weber Jr., J.C. Morriss, J. Sanitary Eng. Div. Am. Soc. Civ.
So suggests a decreased randomness at the solid/solution Eng. 89 (1963) 31.
[32] K.G. Bhattacharyya, A. Sharma, J. Environ. Manage. 71 (3) (2004)
interface and no significant changes occur in the internal 217.
structure of the adsorbent through the adsorption of AB193 [33] J.P. Chen, S. Wu, K.-H. Chong, Carbon 41 (10) (2003) 1979.
onto BTMA-bentonite. [34] I. Langmuir, J. Am. Chem. Soc. 40 (9) (1918) 1361.
[35] H.M.F. Freundlich, Z. Phys. Chem. 57 (1906) 385.
[36] M.M. Dubinin, L.V. Radushkevich, Proc. Acad. Sci. U.S.S.R. Phys.
Chem. Sect. 55 (1947) 331.
References [37] A. Benhammou, A. Yaacoubi, L. Nibou, B. Tanouti, J. Colloid Inter-
face Sci. 282 (2) (2005) 320.
[1] A. Bhatnagar, A.K. Jain, J. Colloid Interface Sci. 281 (1) (2005) 49. [38] J.P. Hobson, J. Phys. Chem. 73 (8) (1969) 2720.
[2] R. Gong, Y. Ding, M. Li, C. Yang, H. Liu, Y. Sun, Dyes Pigments [39] S.M. Hasany, M.H. Chaudhary, Appl. Radiat. Isot. 47 (4) (1996)
64 (3) (2005) 187. 467.
[3] A.S. Ozcan, B. Erdem, A. Ozcan, J. Colloid Interface Sci. 280 (1) [40] S.S. Dubey, R.K. Gupta, Sep. Purif. Technol. 41 (1) (2005) 21.
(2004) 44. [41] F. Helfferich, Ion Exchange, McGraw-Hill, New York, 1962.
[4] M.S. Chiou, H.Y. Li, Chemosphere 50 (8) (2003) 1095. [42] M.S. Onyango, Y. Kojima, O. Aoyi, E.C. Bernardo, H. Matsuda, J.
[5] S. Sohn, D. Kim, Chemosphere 58 (1) (2005) 115. Colloid Interface Sci. 279 (2) (2004) 341.
[6] S.J. Allen, G. McKay, J.F. Porter, J. Colloid Interface Sci. 280 (2) [43] T.W. Webi, R.K. Chakravort, J. Am. Inst. Chem. Eng. 20 (2) (1974)
(2004) 322. 228.
[7] N. Kannan, M.M. Sundaram, Dyes Pigments 51 (1) (2001) 25. [44] K.R. Hall, L.C. Eagleton, A. Acrivos, T. Vermeulen, Ind. Eng. Chem.
[8] P.K. Malik, Dyes Pigments 56 (3) (2003) 239. Fundam. 5 (2) (1966) 212.
[9] C. Namasivayam, D. Sangeetha, J. Colloid Interface Sci. 280 (2) [45] J.-Q. Jiang, C. Cooper, S. Ouki, Chemosphere 47 (7) (2002)
(2004) 359. 711.
[10] A.S. Ozcan, S. Tetik, A. Ozcan, Sep. Sci. Technol. 39 (2) (2004) [46] M.J. Jaycock, G.D. Parfitt, Chemistry of Interfaces, Ellis Horwood
301. Ltd., Onichester, 1981.
[11] R.G. Harris, J.D. Wells, B.B. Johnson, Colloids Surf. A: Physic- [47] B.S. Chu, B.S. Baharin, Y.B. Che Man, S.Y. Quek, J. Food Eng. 62
ochem. Eng. Aspect 180 (12) (2001) 131. (1) (2004) 97.
[12] C.-C. Wang, L.-C. Juang, T.-C. Hsu, C.-K. Lee, J.-F. Lee, F.-C. [48] Y. Yu, Y.Y. Zhuang, Z.H. Wang, J. Colloid Interface Sci. 242 (2)
Huang, J. Colloid Interface Sci. 273 (1) (2004) 80. (2001) 288.