Microporous and Mesoporous Materials 101 (2007) 388396

www.elsevier.com/locate/micromeso

Adsorption kinetics and thermodynamics of an anionic

dye onto sepiolite
zkan Demirbas *, Mehmet Dogan
Mahir Alkan, O
Balikesir University, Faculty of Science and Literature, Department of Chemistry, 10145 Balikesir, Turkey
Received 18 July 2006; received in revised form 2 December 2006; accepted 4 December 2006
Available online 23 January 2007

Abstract
The adsorption kinetics of CI reactive blue 221 (RB221), an anionic dye, onto sepiolite was investigated in aqueous solution in a batch
system with respect to stirring speed, contact time, initial dye concentration, pH, and temperature. Experimental results have shown that
the acidic pH, increasing initial dye concentration and temperature favours the adsorption. Experimental data related to the adsorption
of RB221 on sepiolite under dierent conditions were applied to the pseudo-rst-order equation, the pseudo-second-order equation and
the intra-particle diusion equation, and the rate constants of rst-order adsorption (k1), the rate constants of second-order adsorption
(k2) and intra-particle diusion rate constants (kint) were calculated, respectively. The experimental data tted very well the pseudo-second-order kinetic model and also followed the intra-particle diusion model up to 20 min, whereas diusion is not only the rate controlling step. The activation energy of system (Ea) was calculated as 7.73 kJ mol1. The thermodynamics parameters of activation such as
Gibbs free energy, enthalpy, entropy were also evaluated and found that DG*, DH*, and DS* are 47.9 (49.4, 50.0, 51.3) kJ mol1, 5.30
(5.21, 5.13, 5.05) kJ mol1, and 145.3 (148.8, 142.7, 143.1) J K1 mol1 at 20 (30, 40, 50) C, respectively. The results indicate that
sepiolite could be employed as a low-cost material for the removal of textile dyes from euents.
 2006 Elsevier Inc. All rights reserved.
Keywords: Adsorption; Sepiolite; CI reactive blue 221; Dye; Kinetic models

1. Introduction
The treatment of textile waste comprising of dyestus
and other non-biodegradable organics and inorganic poses
considerable problems in the wastewater treatment industry. Conventional primary and secondary processes are
insucient in removing these contaminants, with the
majority of the research in this eld conducted using tertiary treatments [1]. Reactive dyes are the most common
dyes used due to their advantages, such as bright colours,
excellent colourfastness and ease of application [2,3]. They
exhibit a wide range of dierent chemical structures, primarily based on substituted aromatic and heterocyclic
groups. A large number of reactive dyes are azo com*

Corresponding author. Tel.: +90 266 612 1278; fax: +90 266 612 1215.
E-mail addresses: malkan@balikesir.edu.tr (M. Alkan), ozkan@bali . Demirbas), mdogan@balikesir.edu.tr (M. Dogan).
kesir.edu.tr (O
1387-1811/$ - see front matter  2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2006.12.007

pounds that are linked by an azo bridge [4]. Many reactive

dyes are toxic to some organisms and may cause direct
destruction of creatures in water [5]. In addition, since reactive dyes are highly soluble in water, their removal from
euent is dicult by conventional physicochemical and
biological treatment methods [6,7]. In general, there are ve
main methods of reducing colour in textile euent streams:
adsorption, oxidationozonation, biological treatment,
coagulationocculation, and membrane processes [8,9].
Adsorption phenomenon in solution systems plays a
vital role in many areas of practical environmental technology, which are mainly in water and wastewater treatment
due to several advantages such as high eciency, simple
operation and easy recovery/reuse of adsorbent [1].
Amongst the numerous techniques of dye removal, adsorption is a procedure of choice for the removal of dissolved
organic compounds from wastewater. Adsorption has a
specic advantage of removing the complete dye molecule,

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

389

Nomenclature
qe
R2
t
T
W
qt
C0
k1
k2

equilibrium dye concentration on adsorbent,

mol g1
linear regression coecient
time, s
temperature, K
mass of adsorbent, g
the amount of dye adsorbed per unit mass of the
adsorbent at time t, mol g1
initial dye concentration in aqueous solution,
mol l1
adsorption rate constant for pseudo-rst-order
kinetic equation, s1
adsorption rate constant for pseudo-secondorder kinetic equation, g mol1 min1

unlike certain removal techniques, which destroy only the

dye chromophore leaving the harmful residual moieties in
the euent [10]. Activated carbon is widely used as an
adsorbent due to its high surface area, high adsorption
capacity, but it is relatively high price, which limits their
usage [11]. For this reason, many researchers have investigated low-cost, locally available, biodegradable substitutes
made from natural sources to remove dyes from wastewater [1215]. Clays, such as sepiolite [1618], zeolite [19],
montmorillonite [20], perlite [2123] and bentonite [24,25]
are being considered as alternative low-cost adsorbents.
Sepiolite, which forms an important group of clay minerals, is a natural hydrated magnesium silicate, (Si12)
(Mg8)O30(OH6) (OH2)4 8H2O and currently used in a
number of dierent applications such as many industrial,
catalytic and environmental applications. Structurally, it
is formed by blocks and channels extending in the bre
direction. A signicant number of silanol (SiOH) groups
are present at the surface of these minerals [26]. The presence and concentration of surface functional groups plays
an important role in the adsorption capacity and the
removal mechanism of the adsorbates [27]. Because of their
structural morphology, sepiolites have received considerable attention with regard to the adsorption of organics
on the clay surfaces and to their use as support for catalysts
[28]. The abundance and availability of sepiolite mineral
reserves as a raw material source and its relatively low cost
guarantee its continued utilization in the future, and most
of the world sepiolite reserves are found in Turkey [16].
Several studies were achieved using sepiolite as an adsorbent including catalyst support, wastewater treatment,
solid wastes, reducing the toxic eect of some heavy metals
and pesticides [29]. Most literature on dye removal is
related to cationic dyes. To our knowledge, compared with
cationic dyes, only a little information exists on the use of
sepiolite, as an adsorbent for the removal of anionic dyes
and also needs to research. The water-soluble anionic dyes
are commonly used to dye fabrics like wool, nylon and silk.

t1/2
kint
Ct
Ea
Rg
k0
kB
h
DG*
DH*
DS*

the half-adsorption time of dye, s

intra-particle
diusion
rate
constant,
mol s1/2 g1
dye concentration in solution at any time t,
mol l1
activation energy, kJ mol1
gas constant, J K1 mol1
Arrhenius factor, g mol1 s1
Boltzmanns constant
Plancks constant
free energy of activation, kJ mol1
enthalpy of activation, kJ mol1
entropy of activation, J K1 mol1

Due to 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
sepiolite as an adsorbent [1618,30], but none of them has
investigated the kinetics and thermodynamics of adsorption of RB221 onto sepiolite. In this study, it has been
investigated the adsorption kinetics of CI reactive blue
221 (RB221), a anionic dye, on sepiolite from aqueous
solutions as a function of stirring speed, contact time,
initial dye concentration, pH and temperature. The experimental data were analyzed using pseudo-rst and secondorder kinetics models, and intra-particle diusion models.
Furthermore, activation thermodynamics parameters were
calculated. Results of this study will be useful for future
scale up using this material as a low-cost adsorbent for
the removal of anionic dyes.
2. Material and methods
2.1. Sepiolite
RB221 was selected as a model reactive dye and
obtained from Setas and Eksoy Textile Co. (Bursa, Turkey). The chemical structure of RB221 is shown in Fig. 1.
Sepiolite was obtained from Eskisehir, Turkey. The chemical composition of the sepiolite found in Turkey is given in
Table 1; the cation exchange capacity (CEC), density and
specic surface area in Table 2 [17].

NHC 2H 5

SO 2CH2CH2OSO3H
Fig. 1. The structure of CI RB221.

390

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

separation time on the amount of adsorbed dye was negligible. The absorbency of dye was measured three times for
each sample with a Cary j1Ej UVVis spectrophotometer
(Varian) at 602 nm wavelength, at which the maximum
absorbency occurred. The amounts of dye adsorbed on
sepiolite at any time, t, were calculated from the concentrations in solutions before and after adsorption. At any
times, the amount of RB221 adsorbed (mol g1) (qt), onto
sepiolite was calculated from the mass balance equation as
follows:

Table 1
Chemical composition of sepiolite
Component

Weight %

SiO2
MgO
CaO
Al2O3
Fe2O3
NiO
LoI

53.47
23.55
0.71
0.19
0.16
0.43
21.49

LoI: Loss of ignition.

qt C 0  C e
Table 2
Some physicochemical properties of sepiolite
Colour

Cation exchange
capacity
(meq 100 g1)

Density
(g cm3)

Specic surface
area (m2 g1)

Particle
size (lm)

White

25.00

2.55

342

75

V
W

where qt is the amount of adsorbed dye on sepiolite at any

time (mol g1); C0 and Ce are the initial and equilibrium
liquid-phase concentrations of RB221 (mol l1), respectively; V is the volume of RB221 solution (l), and W is
the mass of sepiolite sample used (g) [3234].
3. Results and discussion

2.2. Purication of sepiolite

3.1. Adsorption rate
Sepiolite was treated before using in the experiments as
follows [31]: the suspension containing 10 g l1 sepiolite
was mechanically stirred for 24 h, after waiting for about
2 min, the supernatant suspension was ltered through lter paper. The solid sample was dried at 105 C for 24 h,
ground then sieved by 75 lm sieves. The particles under
75 lm were used in further experiments.
2.3. Method

To design an eective and quick adsorption model it was

considered necessary to carry out adsorption with kinetics
viewpoint and eects of contact time, stirring speed, initial
dye concentration, pH and temperature on the uptake rate
of the dye were monitored very carefully. The kinetic
adsorption data was processed to understand the dynamics
of adsorption process in terms of the order of rate
constant.

RB221 was dried at 110 C for 2 h before use in experiments. All solutions of RB221 were prepared with distilled
water. The adsorption kinetics of RB221 onto sepiolite was
carried out from its solution. For the experiments of
adsorption kinetics, 2 g sepiolite sample was added into a
liter of RB221 solution at desired concentration, pH and
temperature. The pH of the solution was adjusted with
NaOH or HCl solution by using an Orion 920A pH-meter
with a combined pH electrode. pH-meter was standardized
with NBS buers before every measurement. A preliminary
experiment revealed that about 120 min periods is required
for the adsorption process to reach the equilibrium concentration. A magnetic stirrer at 20 C and 500 rpm for
120 min continuously agitated the mixture. Preliminary
experiments showed that stirring speed has no important
eect on adsorption rate. Therefore, the experiments made
at 500 rpm. The eect of temperature on the adsorption
rate has been studied at 20, 30, 40 and 50 C. A constant
temperature bath was used to keep the temperature constant. At the end of the adsorption period, the solution
was centrifuged for 15 min at 5000 rpm. The samples at
appropriate time intervals were pipetted from the reactor
by the aid of the very thin point micropipette, which prevents the transition to solution of sepiolite sample. Preliminary experiments had shown that the eect of the

3.1.1. Eect of contact time and initial dye concentration

The initial concentration provides an important driving
force to overcome all mass transfer resistances of the dye
between the aqueous and solid phases. The eect of concentration on contact time was also investigated as a function of initial dye concentration. The eect of initial dye
concentration and contact time on the removal rate of
RB221 by sepiolite is shown in Fig. 2. As shown, the
adsorption increases with increasing initial RB221 concentration. The removal of dye depends on the concentration
of the dye. Again, adsorption increased with an increase
in contact time. The equilibrium was attained at 120 min.
Similar result was found for the adsorption kinetics of
malachite green onto activated carbon prepared from
Tuncbilek lignite [35]. The amount of RB221 adsorbed
at equilibrium increases from 2.350 106 to 3.584
106 mol/g by increasing initial RB221 concentration from
2.5 105 to 10 105 mol/l under conditions of initial pH
3 and 20 C. The results show that dye uptake is rapid for
the rst 20 min and thereafter it proceeds at a slower rate
and nally attains saturation. The initial rapid phase may
be due to increased the number of vacant sites available
at the initial stage, as a result there exist increased concentration gradient between adsorbate in solution and adsorbate in the adsorbent [36]. Generally, when adsorption

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

surface [37]. In clay-aqueous systems, the potential of the

surface is determined by the activity of ions (e.g., H+ or
pH), which react with the mineral surface. For clay minerals the potential determining ions are H+ and OH and
complex ions formed by bonding with H+ and OH [38].
It is remarkably noted from zeta potential measurements
that sepiolite has an isoelectrical point at pH 6.6 [39]. In
this case, sepiolite surface has positive zeta potential below
pHiep and negative zeta potential above pHiep. The broken
bonds along the surface of the clay crystals result in hydrolysis. In acid medium, the positive charge develops on the
surface of adsorbent and may be written as [3234]

3.75
3.50

q t (mol g-1)x10

3.25
3.00
2.75
2.50

@SOOH H
@SOOH
2

2.25
C0 (mol L-1)x105
: 10.0
: 7.5
: 5.0
: 2.5

2.00
pH
T

: 3.0
: 20 C

1.75
0

20

40

60
t (min)

80

100

120

Fig. 2. The eect of contact time and initial concentration on the removal
rate of RB221 onto sepiolite from aqueous solutions.

involves a surface reaction process, the initial adsorption is

rapid. Then, a slower adsorption would follow as the available adsorption site gradually decreases.
3.1.2. Eect of pH
Eect of pH on the removal rate of RB221 is shown in
Fig. 3. As the pH increased, the removal rate decreased.
The pH value of the dye solution plays an important role
in the whole adsorption process and particularly on the
adsorption capacity. Similar observations have been
reported by other workers for adsorption of reactive dyes
indicating that the carbon has a net positive charge on its
2.50

2.25
qt (mol g-1) x 106

391

2.00

1.75

T
C0

pH
: 3
: 5
: 7
: 9

: 20 C
: 2.5x10-5 mol L-1

1.50
0

20

40

60
t (min)

80

100

120

Fig. 3. The eect of contact time and initial pH on the removal rate of
RB221 onto sepiolite from aqueous solutions.

As can also be seen in Eq. (2), as the pH of the dye solutions becomes lower than pH 6.6, the association of dye
anions with more positively charged sepiolite surface
because of increasing SOOH
2 groups could more easily
take place. Since the solution is acidied by hydrochloric
acid, the outer surface of positively charged interface will
be associated with Cl ions. The chloride ions are
exchanged with dye ions.



@SOOH
2 Dye
@SOOH2 Dye

This can also be explained as follows: at low pH, sepiolite surface is closely associated with the hydronium
(H3O+) ions. The surface of sepiolite becomes positively
charged, thereby increasing electrostatic attractions
between negatively charged dye anions and positively
charged adsorption sites and causing an increase in the
dye adsorption. With the gradual increase in the pH of
the solution, a decrease in the positive charge on the oxide
or solution interface has been observed and the adsorbent
surface appears negatively charged due to deprotonation
of the adsorbent surface. The removal of dye decreases at
higher pH values may be due to the abundance of OH
ions and because of electrostatic repulsion between the
negatively charged surface of adsorbent and the anionic
dye molecules [40].
3.1.3. Eect of temperature
A study of the temperature dependence of adsorption
reactions gives valuable knowledge about the enthalpy
and entropy changes during adsorption. Fig. 4 exhibits
contact time versus adsorbed amount graph at dierent
temperatures. The equilibrium adsorption capacity of
RB221 onto sepiolite was found to increase with increasing
temperature, increasing from 3.521 106 mol g1 at 20 C
to 4.360 106 mol g1 at 40 C indicating that the dye
adsorption on the adsorbent was favored at higher temperatures. The fact that the adsorption rate of RB221 onto
sepiolite at various temperatures increases may be due to
an increase in the mobility of RB221 ions with an increase
in the temperature in the solution [41,42]. This eect suggests that an explanation of the adsorption mechanism
associated with the removal of RB221 onto sepiolite
involves a physical process. A further verication of the

3.2. Adsorption kinetics

Calculated
qe 106
(mol g1)

Several kinetic models are used to examine the controlling mechanism of adsorption process such as chemical
reaction and diusion control.

3.2.3. Intra-particle diusion

An empirically found functional relationship, common
to the most adsorption processes, is that the uptake varies

First-order

0.999
1.000
0.998
1.000
0.999
1.000
0.999
0.999
0.996
0.999
8.1
11.5
17.7
18.5
6.1
6.6
3.1
10.5
20.6
45.0
0.999
1.000
0.999
0.998
0.998
0.999
1.000
1.000
0.998
0.998
56.0
88.8
123.1
126.5
41.0
51.4
48.3
154.2
190.0
216.5
0.999
0.998
0.999
1.000
0.999
0.999
0.999
1.000
0.999
0.999
2.5
5.0
7.5
10.0
2.5
2.5
2.5
10.0
10.0
10.0

where k2 is the second-order constant (g/mol min) and can

be determined experimentally from the slope and intercept
of plot t/qt versus t.

20
20
20
20
20
20
20
30
40
50

pH

t
1
1

t
2
qt k 2 qe qe

Concentration
105 (mol l1)

3.2.2. The second-order kinetic model

The second-order kinetic model is expressed as [44]

Temperature
(C)

where qe and qt are the amounts of dye adsorbed (mol/g) at

equilibrium and at time t (min), respectively, and k1 is the
rate constant of adsorption (min1). The values of k1 and
correlation coecients at dierent conditions are presented
in Table 3.

Second-order

4
Table 3
Kinetics values calculated for RB221 adsorption onto sepiolite

lnqe  qt ln qe  k 1 t

Experimental
qe 106
(mol g1)

3.2.1. The rst-order kinetic model

The rate constant of adsorption is determined from the
rst-order rate expression given by Lagergren and Svenska
[43].

103.0
136.1
262.2
275.3
84.7
75.3
68.1
251.1
300.6
392.4

kdif-1 103
(mol min1/2 g1)

endothermic nature of the process was done by calculating

the half-life of process at each temperature, which was
found to increase with increasing temperatures (Table 3).

2.384
2.810
3.220
3.584
2.135
2.082
2.052
3.792
4.020
4.522

Fig. 4. The eect of contact time and temperature on the removal rate of
RB221 onto sepiolite from aqueous solutions.

2.350
2.774
3.167
3.521
2.120
2.060
2.020
3.700
3.910
4.360

120

1.231
1.813
2.441
2.697
1.006
0.874
0.640
3.001
3.269
3.638

100

k2 105
(g mol1
min1)

80

R2

60
t (min)

k1 102
(min1)

40

R2

20

Intra-particle diusion
(kdif)

R2

2.40

kdif-2 103
(mol min1/2 g1)

R2

pH : 3.0
C0 : 10x10-5 mol L-1

0.999
1.000
1.000
0.999
1.000
0.999
0.999
0.999
0.999
0.999

2.70

Temperature ( C)
: 50
: 40
: 30
: 20

4.91
8.95
7.91
9.05
4.93
4.89
4.18
5.41
6.40
6.29

3.00

0.999
0.946
0.971
0.934
0.998
0.994
0.977
0.956
0.997
0.998

3.30

3
3
3
3
5
7
9
3
3
3

R2

3.60

kdif-3 103
(mol min1/2 g1)

-1
qt (mol g ) x 10

3.90

0.491
0.503
0.518
0.670
0.550
0.652
0.602
0.570
0.687
0.675

Mass
transfer

4.20

R2

4.50

2.138
2.284
2.293
2.549
1.497
1.778
1.800
2.970
3.196
3.419

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

t1/2 (min)
(for secondorder)

392

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

almost proportionally with t1/2, the WeberMorris plot,

rather than with the contact time t [45].
qt k int t1=2 C

60
C0 (mol L-1)x105
: 2.5
: 5.0
: 7.5
pH
: 10.0
T

-6

40

-1

t/qt (min g mol )x10

: 3.0
: 20 C

30
20
10
0
0

20

40

60
t (min)

80

100

120

Fig. 5. Second-order kinetic equation for adsorption of RB211 on

sepiolite at dierent initial dye concentrations.

:
:
:
:

50
t/qt (min g mol-1)x10-6

pH
3
5
7
9

40

T : 20 C
C0 : 2.5x10-5 mol L-1

30
20
10
0
0

20

40

60
t (min)

80

100

120

Fig. 6. Second-order kinetic equation for adsorption of RB221 on

sepiolite at dierent initial pHs.

40
Temperature ( C)
: 50
: 40
: 30
pH : 3.0
: 20
C0 : 10x10-5 mol L-1

-6

35

-1

t/qt (min g mol )x10

3.2.4. Kinetics analysis

The kinetic parameters for adsorption of RB221 under
dierent conditions were calculated from Eqs. (4)(6) and
are given in Table 3. The correlation coecients (R2), for
the rst-order kinetic model are between 0.934 and 0.999,
and the correlation coecients (R2), for the pseudo-second-order kinetic model are in the range of 0.9991.000.
Again, the experimental qe values agree with the calculated
ones, obtained from the linear plots (Table 3). Calculated
correlation coecients (R2) are closer to unity for second-order kinetics model; therefore the adsorption kinetics
could well be approximated more favorably by secondorder kinetic model for RB221 adsorption, based on the
assumption that the step may have chemisorption, provides
the best correlation of the data. The k2 (g/mol min) and R2
values were calculated from Figs. 57 and listed in Table 3.
Similar phenomena have been observed in the biosorption
of remazol black B on biomass [47], adsorption of congo
red [48] and 2-chlorophenol [49] on coir pith carbon and
the adsorption of methylene blue on perlite [34]. Moreover,
the pseudo-second-order rate constants indicate a steady
increase from 1.231 105 to 3.638 105 g mol1 min1
with an increase in the solution temperatures from 20 to
50 C (Table 3).
For intra-particle diusion model, Ho [50] pointed out
that it is essential for the qt versus t1/2 plots to go though
the origin if the intra-particle diusion is the sole rate limiting step. Generally, if the adsorption steps are indepen-

50

60

where kint is the intra-particle diusion rate constant.

According to Eq. (6), a plot of qt versus t1/2 should be a
straight line with a slope kint and intercept C when adsorption mechanism follows the intra-particle diusion process
[46].

393

30
25
20
15
10
5
0
0

20

40

60
t (min)

80

100

120

Fig. 7. Second-order kinetic equation for adsorption of RB211 on

sepiolite at dierent temperatures.

dent of one another, the plot of qt versus t1/2 usually

shows two or more intercepting lines depending upon the
exact mechanism [51]. The intra-particle diusion plots
for the eect of pH are given in Fig. 8 (other gures not
shown). Table 3 shows the corresponding model tting
parameters. In the present study, any plot did not passed
through the origin. The plots present multilinearity, indicating that three steps take place. The rst, sharper portion
is attributed to the diusion of adsorbate through the solution to the external surface of adsorbent or the boundary
layer diusion of solute molecules. The second portion
describes the gradual adsorption stage, where intra-particle
diusion is rate limiting. The third portion is attributed to
the nal equilibrium stage [52]. Values of the intra-particle
diusion constants (kint1, kint2 and kint3) were obtained
from the slopes of the linear portions of the plots and are
listed in Table 3. The correlation coecients for the
intra-particle diusion model (R2) were 0.996 and 1.000.
These values indicate that the adsorption of RB221 onto
sepiolite may be followed by an intra-particle diusion up

394

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

2.40

12.9
C0
pH

kint3

2.30

: 1.0x10-4 M
:3

12.8

kint2

12.7
lnk2

qt (mol g-1)x106

2.20

2.10

12.6

kint1

2.00

12.5
1.90

12.4
3.00

pH
: 3
: 5
: 7
: 9

1.80
20 C

T :
C0 : 2.5x10-5 mol L-1

3.13

3.25

3.38

3.50

1/T (K-1)x103

Fig. 9. Arrhenius plots for adsorption of RB211.

1.70
2

8
1/2

t (min)

10

12

1/2

Fig. 8. Intra-particle diusion plots for adsorption of RB221 onto

sepiolite at dierent pHs.

to 20 min. This indicates that although intra-particle diusion was involved in the adsorption process, it was not the
rate-controlling step. The values of kint increased with
increasing initial RB221 concentration. The driving force
of diusion is very important for adsorption processes.
Generally, the driving force changes with the adsorbate
concentration in the bulk solution. The increase of adsorbate concentration results in an increase of the driving
force, which will increase the diusion rate of RB221.
A comparison between the adsorption orders and models of basic dyes on various adsorbents are present in Table
4. As seen in Table 4, similar results were found for basic
red 22 on pith, for methylene blue on perlite and for methylene blue on y ash.
3.3. Activation thermodynamic parameters
Because the k2 values have been determined, several
thermodynamic parameters including the Arrhenius activa-

tion energy (Ea), activation free energy change (DG*), activation enthalpy change (DH*), and activation entropy
change (DS*) can be calculated by using the following
equations [34]:
ln k 2 ln A 

Ea
RT

kB T 
K
h
DG RT ln K 
DH  Ea  RT
DH   DG
DS 
T
ln k 2

8
9
10
11

where A is the Arrhenius factor, kB and h are Boltzmanns

and Plancks constants, respectively, R is the gas constant,
and K* is the equilibrium constant at temperature T. A linear plot of ln k2 versus 1/T for the adsorption of RB221
onto sepiolite is constructed to generate the Ea value
from the slope (Fig. 9). The result obtained is 7.73 kJ mol1
with a linear regression coecient 0.9973. Moreover, the
values of DG*, DH*, and DS* are 47.9 (49.4, 50.0, 51.3)
kJ mol1, 5.30 (5.21, 5.13, 5.05) kJ mol1, and 145.3

Table 4
Adsorption order and mechanism of some dyes on various adsorbents
Adsorbents

Reaction order

Adsorbates

Adsorption mechanism

Ref.

Fly ash
Biosorbent
Bottom ash
Calcined alunite
Bagasse y ash
Activated carbon
Pith
Wood
Perlit
Perlit
Perlit
Modied peatresin particle
Sepiolite

Pseudo-second-order
Pseudo-rst-order
Pseudo-rst-order
Pseudo-second-order
Pseudo-second-order
First order
Pseudo-second-order

Pseudo-second-order
Pseudo-second-order
Pseudo-second-order

Pseudo-second-order

Methylene blue
Methylene blue
Quinoline yellow
Reactive dyes
Orange-G, Methyl violet
Methylene blue
Basic red 22
Astrazon blue
Methylene blue
Methyl violet
Victoria blue
Basic dyes
RB221

Particle diusion

Mass transfer

Intra-particle diusion
Intra-particle diusion
Intra-particle diusion
Intra-particle diusion
Intra-particle diusion

Intra-particle diusion

[53]
[54]
[55]
[7]
[56]
[46]
[57]
[58]
[34]
[32]
[33]
[59]
In this study

M. Alkan et al. / Microporous and Mesoporous Materials 101 (2007) 388396

(148.8, 142.7, 143.1) J K1 mol1 at 20 (30, 40, 50) C,

respectively.
The low DH* values for RB221 give a clear evidence that
the interactions between RB221 and the surface hydroxyl
groups of sepiolite may be weak. On the other hand, the
positive values of Ea, DG*, and DH* indicate the presence
of an energy barrier in the adsorption process. The positive
values for these parameters are quite common because the
activated complex in the transition state is in an excited
form. The negative values of DS* suggest decreased randomness at the solid/solution interface and no signicant
changes occur in the internal structure of the adsorbent
through the adsorption of RB221 onto sepiolite.
3.4. Conclusions
Sepiolite has proved to be an eective adsorbent for the
removal of anionic dye via adsorption from aqueous solution. Equilibrium adsorption was achieved in about 2 h.
The adsorption is highly dependent on concentration, pH
and temperature of the solution. pH aects the surface
charge of the adsorbent and the degree of ionization of
adsorbate. Adsorption kinetic follows pseudo-secondorder kinetic model conrming the chemisorption of
RB221 onto sepiolite. By second-order model to study
the mechanism of adsorption, calculated qe values agreed
well with the qe experimental values. Kinetic results showed
that the adsorption is a three-stage process comprising a
fast initial phase, a second slow and then a slower third
phase. In the rst phase, RB221 is adsorbed at the outer
sites of the adsorbent particles in a fast process that dominates the initial kinetics of adsorption. In the second and
third phases, dye molecules slowly diuse inward and
adsorb to the inner sites of the adsorbents. The temperature eect was also used to calculate the thermodynamic
activation enthalpy, entropy, and free energy of adsorption. The analysis of these thermodynamic parameters suggested that the adsorption is mainly physical because of the
low adsorption activation enthalpy.
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