Journal of Environmental Chemical Engineering 1 (2013) 496503

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Adsorption kinetics of some textile dyes onto granular activated carbon

Kumar Djamel Belaid a, Smal Kacha a,*, Mostefa Kameche b, Zoubir Derriche b
a
b

Laboratory of Materials and Reactive Systems (LMRS), Djillali Liabes University of Sidi Bel-Abbes, P.O. Box 89, 22000 Sidi Bel-Abbes, Algeria
Laboratory of Physical-Chemistry of Materials, Faculty of Sciences, University of Sciences and Technology of Oran, MNouar 1505, 31000 Oran, Algeria

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 5 March 2013
Received in revised form 2 May 2013
Accepted 7 May 2013

Adsorption kinetics of Acid Blue 113 (AB), Basic Red 5 (BR) and Reactive Yellow 81 (RY) textile dyes were
studied. The investigations were essentially conducted to determine the inuence of the initial dye
concentration of aqueous solutions on the adsorption kinetics. The experiments, carried out in a batch
reactor, allowed the determination of the equilibrium times (1 h for RY and AB and 4 h for BR). The
experimental data were analyzed according to the surface reaction and intra-particle models. In effect,
the adsorption results were perfectly tted to the pseudo-second order, with very high regression
coefcients (r2), predicting a signicant intra-particle diffusion stage in the controlling of the adsorption
process. Moreover, the tting to Elovich equation, conrms that the process is ensured by chemisorption
on a highly heterogeneous material.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Textile dyes
Aqueous solutions
Granular activated carbon
Adsorption
Kinetics

Introduction
The wastewater treatment is required by various obligations
which are environmental or concerning with public health. Dye
wastewaters represent the most amounts of the discharged
industrial water [1]. The test, application and development of
many treatment methods were the essential subjects of many
articles. They can be physical, chemical or biological [24].
Biodegradation and adsorption were the two treatments widely
used in the purication of waters [5,6]. The treatment by
adsorption consists of the retention of dyes onto a solid material
called adsorbent by chemical or/and physical bonding. Several
solid adsorbent materials such as activated carbon [7], clays [8],
zeolite [9], biomasses [10], and industrial waste products [11] are
able to remove efciently color from water.
Commercial activated carbons are the most adsorbent materials
used in the water treatment [12]. They are obtained from various
resources, including rattan sawdust [13], coconut husk [14], cattail
[15], etc. They are physically or chemically activated at high
temperature [16] in order to confer them porous structure,
chemical surface function and important adsorption properties
[17].
Textile dyes are the essential cause of color in the discharged
wastewaters [18]. Dye molecules present a considerable structural
diversity, allowing them to be classied by several manners [19]:
either according to their chemical structures or their applications
with suitable type of ber. They can also be classied with respect

* Corresponding author. Tel.: +213 567 577; fax: +213 544 344.
E-mail address: smail_k@yahoo.fr (S. Kacha).
2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.05.003

to their solubility in water [8]. Acid, basic, reactive and direct dyes
are soluble dyes, while dispersed pigments and oxidized dyes are
insoluble in water.
Adsorption kinetics describe the reduction of the aqueous
adsorbate concentration from solution according to the reaction
time variation. During the adsorption process, four distinct stages
are considered. The transport of the aqueous adsorbate until the
lm surrounds the particle surface of the adsorbent (this rst stage
can be neglected if the system is perfectly stirred); the external
diffusion (the second stage); the intra-particle diffusion (the third
stage) and the physical or chemical surface reactions (the fourth
stage). These stages can be compared to a succession of resistance
phenomenon to the mass transfer of the adsorbate from the
solution medium until the adsorption sites of the adsorbent
(Fig. 1). One or two of these stages can be kinetically determining.
Ho and McKay [20] consider that only the external and intraparticle lm diffusions control the kinetics of adsorption.
Although the adsorption of dye removal from solutions was
sufciently studied by many authors, it was observed that the
several studies were devoted for one type of dyes. Nandi et al. [1]
studied the removal of cationic dyes from aqueous solutions by
kaolin. Shi et al. [3] studied the removal of direct dyes by
preformed polymeric aluminum species. Kacha et al. [8] studied
the equilibrium and kinetics of color removal from acid dye
solutions with bentonite and polyaluminum hydroxide. Orfao et al.
[17] studied the adsorption of a reactive dye on chemically
modied activated carbons. It is, thus, interesting to check the
behavior of structurally different dyes belonging to various groups
with the same adsorbent material. In this work, a commercial
granular activated carbon was used as adsorbent to remove from
water three textile dyes namely Acid Blue 113, Basic Red 5 and

K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

497

Nomenclature

a
k1
C0
Ce
C
De
F(t)
H
k2
kF
kid
kL
m
ms
q0
qe
qt
R
SS
V

coefcient related to the extension of covered

surface and chemi-sorption activation energy
(g mg1)
rate of chemi-sorption (mg g1 min1)
pseudo-rst order rate constant (min1)
initial dye concentration (mg/L)
equilibrium dye concentration in liquid phase (mg/
L)
a constant
diffusivity of aqueous salt (m2/s)
fraction of salt on adsorbent
initial sorption rate (mg g1 min1)
pseudo-second order rate constant (g mg1 min1)
external coefcient of mass transfer (m min1)
intra-particle diffusion rate constant
Langmuir equilibrium constant for carbon/dye
system (L mg1)
mass of the used carbon (g)
adsorbent dosage (=m/V)
initial dye concentration present on solid phase
(mg/g)
adsorption capacity at equilibrium (mg/L)
adsorption capacity at time t (mg/L)
adsorbent particles ray (m)
specic particles area during external mass transfer (cm1)
volume of sample (L)

Reactive Yellow 81. The study was particularly focused on the

inuence of the initial dye concentration on the adsorption
kinetics.
Materials and methods
Materials
Commercially available granular activated carbon (GAC)
purchased from Cheminova International (Spain) was used. The
BET surface area, mean particle size and main characteristics of this
granular activated carbon are listed in Table 1. The mean diameter
of its particles is higher than 2 mm. A quantity of this coal was
initially crushed in a laboratory mortar, then separated by sifting in
order to obtain the fraction of diameter ranging between 1 and
2 mm, washed with distilled water and dried during 48 h in a
drying oven at 383 K, and nally stocked in a desiccator for future
uses.
Two anionic dyes (Acid Blue 113 and Reactive Yellow 81) and
one cationic (Basic Red 5) were considered in this study. These
three soluble dyes can be applied to most synthetic bers and
Table 1
Physicochemical characteristics of granular activated carbon (GAC).
Origin

Charcoal, vegetal activated

Mean particle size (mm)

Surface area (m2/g)
Bulk density (cm3/g)
Iodine value
Ashes (%)
H2O (%)

3
1100
0.425
1050
<12
<10

Fig. 1. External and intra-particle diffusion of adsorbates onto porous adsorbents.

cotton using simple exhaustive techniques. They are mixtures of

molecule dyes (5098%) and several substrates used as additives.
The basic dye possesses a small molecule (M = 288.8 g mol1)
compared to the two others (M = 681.65 and 1631 g mol1,
respectively) and has a different behavior in an aqueous solution.
Physicalchemical specications concerning the dyes (i.e. purity
degree and developed chemical formulae) are sometimes not
communicated by manufacturers. The main characteristics of the
studied dyes are presented in Table 2.
Methods
Dye solutions
The dyes were used as provided by the manufacturer, without
any preliminary purication. The acidic (AB) and basic (BR) dye
solutions were prepared by dissolving 400 mg of dye powder in 1 L
of distilled water. For the reactive dye (RY) existing in a hydrolyzed
form in the textile efuents [21], a dye solution of 600 mg/L was
prepared by the same method described by Pereira et al. [22]. The
dye was hydrolyzed by increasing the temperature to 50 8C, and
adding some salts with sodium hydroxide until the nal pH of the
solution became 12. All solutions with different initial dye
concentrations were prepared from the three indicated solutions
by adding distilled water.
Adsorption kinetics
Adsorption batch experiments were carried out from 1.7 L of
dye solution in a 3-L beaker. The solutions of dyes, used as aqueous
adsorbates, were stirred during 35 h at 550 rpm. In order to
investigate the effect of the initial dye concentration on the
adsorption kinetics, the following concentrations were used: 20,
40, 60 and 80 mg/L (AB and BR); and 32, 65, 95 and 123 mg/L (RY).
The activated carbon amounts were added to prepared solutions.
They were well stirred and kept at 294 K with an air-bath. The
equilibrium was normally reached during 1 h for AB and RY, whilst
4 h for BR. The optimal mass of 3.4 g of the adsorbent (2.0 g L1)
determined separately, the diameters of the particles (1 = 1
2 mm) and the temperature of the bath (294 K) were kept constant
during all the experiments. The initial pHs (67) of the basic
solutions of BR and RY, were adjusted by adding sulfuric acid
solution 0.1 N. This pH range was chosen so that the charge point

K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

498

Table 2
Main characteristics of dyes used with different forms.
Dye

Acidic

Basic

Reactive

Symbol
Commercial name
Generic name
IUPAC name

AB
Acid Blue 113

BR
Neutral Red
C.I. Basic Red 5
Chlorure de 3-amino-7-dimethylamino-2-methylphenazine

RY
Reactive Yellow 81

50040
553-24-2
98%
C15H16N4HCl
288.8
462

CI 2630
59112-78-6

C.I. number
CA.S. number
Dye composition
Linear formula
Molecular weight
UVvis (lmax)
a

Disodium8-anilino-5-[[4-(3-sulfonatophenyl)azo-1naphthyl]azo]naphthalene-1-sulfonate
26360
3351-05-1
50%
C32H21N5O6S22Na
681.65
565 nm

C52H34Cl2N18O20S66Na
1631
350a

Hydrolized dye.

vanished. In effect, for the activated carbon used the pH was 6.7.
This value was determined by the same method cited by Crini [6].
Samples of each solution were taken at regular intervals of time,
then ltered by glass lters (diameter of pores 0.45 mm) and
analyzed to determine their concentration.
The equilibrium dye concentration of solutions were measured
from their absorbances at the maximum absorption wavelength of
each dye, by UVvis spectrophotometer (Ficher Bioblock Scientic
1100, Germany), with retro enlightened LCD screen, equipped by
10 mm tubular cell (Table 1).
In order to quantify the sorbed amounts of dyes onto solid
phase (GAC), being determined from measured concentrations, the
adsorption capacities qe (mg/g) were calculated using (Eq. (1)):

qe

 
V
 C 0  C e q0
m

(1)

where V is the volume of the dye solution (L), m the mass of used
GAC (g), C0 and Ce the initial and the equilibrium concentrations of
dye in the liquid phase (mg/L) and q0 is the concentration of dye
initially present on the solid phase (mg/L).
The pH of the dye solutions was measured using a pH-meter
(InoLab pH Level 1, D-82362 Weillheim, Germany).
Theoretical models
The results were tted to surface reaction and intra-particle
models.
Surface reaction
Pseudo-rst order equation. The pseudo-rst order was often
expressed by Lagergren equation [23] being the most cited
formula [24] (Eq. (2)):

logqe  qt logqe 


k1
t
2:303

(2)

with qe the adsorption capacity at equilibrium (mg/L), qt the

0
adsorption capacity at time t (mg/L) and k1 the pseudo-rst order
constant (min1).
The slope of the linear t of log(qe  qt) versus t allows to
determine the value of (k1/2.303). The intercept of the straightline gives the value of log(qe).
Lagergren equation represents the pseudo-rst order kinetics
for the whole adsorption reaction, with a one-partial order with
respect to the free concentration sites and a zero-partial order with
respect to the solute in the solution.

Pseudo-second order equation. The most mentioned formula to

express the pseudo-second order was indicated by Ho and McKay
[25] by the following expression (Eq. (3)):

  
t
1
1

(3)

t
2
qt
qe
k2 qe
with k2 the pseudo-second order constant (g mg1 min1) and
2
k q2e h the initial sorption rate (mg g1 min1).
The constants of this equation can be determined by plotting
the straight line 1/qt versus t.
In this case, the pseudo-second order kinetics for the whole
adsorption reaction, it may be accepted a two-partial order with
respect to the free sites concentration and a zero partial with
respect to the solute in the solution.
In order to obtain better results in terms of regression
coefcient and comparison between theoretical and experimental
values, certain authors showed that (Eq. (3)) can be exploited
differently with some rearrangements [26].
Elovich equation. Namasivayam and Sangeetha [11] indicated that
the Elovich expression (Eq. (4)) was initially used to describe the
chemisorption kinetics of gases onto solids [27]. In spite of this, it
was widely used and cited in case of chemisorption kinetics of
solid/liquid systems [28]. Currently, Elovich equation has been
generalized and frequently used in the sorption studies of many
pollutants in aqueous solution [29]:
 
 
1
1
(4)
 lnab
 lnt
qt

where a is the chemi-sorption rate (mg g1 min1) and b is a

coefcient in relation with the extension of covered surface and
activation energy of chemi-sorption (g mg1).
The equation constants are tabulated from the plot of the
straight line qt versus ln t.
Diffusion models
External diffusion equation. The kinetic equation presented by
McKay and Allen [30] is often applied to model the external
diffusion, during the migration of aqueous adsorbates from a liquid
phase to the solid adsorbent (Eq. (5)):
   0 


k f  Ss
Ct
A

ln A0 
t
ln
0
C0
ms K L
A

(5)

with KL the Langmuir constant for carbon/dye system (L mg1), Kf

the coefcient of external mass transfer (m min1), Ss the specic
surface of particles during external mass transfer (cm1), ms the
concentration of adsorbent in liquid phase: ms = m/V, with

K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

A0

499

50

ms  K L
1 ms  K L

40

Intra-particle diffusion equation. According to Hamdaoui [29], any

kinetic approach of the intra-particle diffusion may be deduced
successively from works of Weber et al. [31] and Boyd et al. [32]. As
proved recently [33,34], in order to appreciate the role of the intraparticle diffusion in the adsorption process, the following kinetic
expression is used (Eq. (6) or (7)):
qt kid  t 1=2

q e (mg/g)

By plotting ln[(Ct/C0)  (A0 /msKL)] versus time, it is possible to

know if the external diffusion stage is (or not) determinant for the
adsorption process.

30

20

10

(6)
0

or

qt kid  t 1=2 C st

20

40

60

80

100 120 140

(7)

where qt is the sorbed amount of adsorbate per unit of mass of

adsorbent (adsorption capacity at the time t) (mg/L) and kid is the
intra-particle diffusion constant.

160 180 200 220 240

Time (min)
Fig. 3. Effect of initial Basic Red concentration on adsorption capacity of granular
activated carbon. VS = 1.7 L; mad = 3.4 g; 1p = (12 mm); stirring = 500 rpm; pH 6
7; T = 294 K.

Results and discussion

80 mg/L) were found equal to 2.5, 4.0, 5.7 and 7.6 mg/g,
respectively.

Adsorption of the acid dye (AB)

Adsorption of the basic dye (BR)

Fig. 2 shows the effect of the initial dye concentration on the

retention rate of AB onto GAC at increasing contact time. The
variation of extracted dye amounts per unit of mass of adsorbent
(qt) according to the reaction time was mentioned. For the four
used concentrations, the rate of retention increases with the
increasing reaction time, but it follows two different slopes. The
rst, ranging between 20 and 60 min, is fast, whilst the second is
slow. This is explained by the availability of adsorption sites
initially free, which become saturated as time increases. The
retention is, thus, limited. It is known that the equilibrium of
adsorption process in case of porous adsorbents is gradually
reached [35]. According to the obtained results, it may be noticed
that the elimination rate of dyes slightly decreases with the
increasing of the initial dye concentration, while remaining in the
same order (i.e. about 19%) for the various concentrations, except
that of 20 mg/L which exceeds 25%. The adsorption capacities at
equilibrium time (qe), for the used concentrations (20, 40, 60 and

The adsorption kinetics of BR on the GAC was studied using the

same conditions applied in the case of AB; the results concerning
with the variation of qt according to the reaction time are
presented in Fig. 3. The equilibrium of the sorption process is
gradually reached once again, in agreement with the fact that the
activated carbon has a porous structure [35,36]. The pseudoequilibrium time in the case of high dye concentrations was longer
than that of low concentrations, and required more than 2 h of
reaction. When the initial dye concentration increases from 20 to
80 mg/L, the percentage of dye elimination remains almost
constant around 63% except for 20 mg/L (69%). The amounts of
the sorbed dye (qe), for the used concentrations (20, 40, 60 and
80 mg/L) are found 6.7, 12.5, 18.9 and 25.1 mg/g, respectively. The
sorption capacities of BR on GAC are higher than those of AB, and
increase with increasing of initial concentration.

4
12

qe (mg/g)

q e (mg/g)

0
0

20

40

60

80

100

120

140

160

180

Time (min)
Fig. 2. Effect of initial Acidic Blue concentration on adsorption capacity of granular
activated carbon. VS = 1.7 L; mad = 3.4 g; 1p = (12 mm); stirring = 500 rpm; pH 6
7; T = 294 K.

50

100

150

200

250

300

Time (min)
Fig. 4. Effect of initial Reactive Yellow concentration on adsorption capacity of
granular
activated
carbon.
VS = 1.7 L;
mad = 3.4 g;
1p = (12 mm);
stirring = 500 rpm; pH 67; T = 294 K.

K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

500

Table 3
Experimental data and operational conditions of dye adsorption kinetics, at ambient temperature and various initial dye concentrations.
C0 (mg/L)

m/V (g/L)

dpi (mm)

pH

Ce (mg/L)

qe (mg/g)

Acidic Blue

20
40
60
80

12

15.0
32.1
48.3
64.8

2.5
4.0
5.7
7.6

Basic Red

20
40
60
80

12

6
14.8
22.2
29.7

6.7
12.5
18.9
25.1

32
65
94
123

12

30.7
62.1
90.6
117.9

1.1
1.5
2.0
2.5

Reactive Yellow

Adsorption of the reactive dye (RY)

300
32 mg/L
65 mg/L
94 mg/L
123 mg/L
200

t/q t

Fig. 4 shows the results of the adsorption kinetics of RY on the

GAC. The same observations were also made in this case (two
different straight-lines slopes). Nevertheless, the slowest stage
begins about approximately 90 min. During the adsorption process
in aqueous solutions, using porous adsorbents, the consecutive
stages of mass transfer take relatively a long contact time, due to
complex structure of adsorbent [35]. The sorption results of qt
show that the reactive dye has the lowest rate of elimination in the
rst hour of reaction. The percentages of elimination decrease with
increasing of dye concentration, however they remain in the same
order (4%) for the various concentrations, except for that of 32 mg/
L which exceeds 6%. The extracted dye amounts per unit of
adsorbent mass increase from 1.1 mg/g (lowest concentration) to
2.5 mg/g (highest concentration).
The experimental data for the adsorption of the three dyes are
summarized in Table 3. As the results indicate, the initial dye
concentration is a signicant parameter controlling the amount of
extracted dye from water. The sorption capacity increases with
increasing of initial dye concentration, whereas the percentage of
color removal decreases. Under the same operating conditions, the
equilibrium time of adsorption is rstly reached for RY and AB
(anionic dyes). Although the basic dye (BR) required more contact
time to reach equilibrium, it was the best adsorbed dye, while the
reactive dye RY had the lowest rate of elimination. The reactive dye
has a long structural chain (C52) and high molecular weight;
therefore it has the lowest rate of elimination during the rst
minutes. The basic dye having the smallest formula and weight
(C15) was the most adsorbed dye; it is more uid and penetrates
more easily through the pores, taking a long time to reach the
internal surface of the adsorbent. It is known that the activated
carbon is composed by a complex porous internal structure [37],
allowing a slow penetration of adsorbate through the pores. The
equilibrium of adsorption process is, therefore, a function of
contact time. In addition, it was observed that the lowest initial dye
concentration for each dye favors the best elimination. It is known
that the adsorption process is inuenced by the low adsorbate
concentrations (effect of dilution) [38]. This can be explained by
the fact that the weak adsorbate molecules concentration favors
their high mobility. The absence of the molecules inside the pores
facilitated their penetration into the material.

100

120

180

240

300

Time (min)
Fig. 5. Adjustment of Reactive Yellow adsorption to pseudo-second order model at
various initial dye concentrations.

neglected, this model expresses the proportionality between the

reaction rate and the aqueous dye concentration. It was found that
this model was not suitable for the three considered systems (GAC/
AB), (GAC/BR) and (GAC/RY). This behavior is was expected if the
external diffusion is not the determining step in the adsorption
process because since its linear expression has a similar form as
that of the traditional model of external diffusion. Besides, the
pseudo-rst order was generally used in case of physical
adsorption onto homogeneous adsorbents [39].

Table 4
Pseudo-second order parameters of dye adsorption onto granular activated carbon
at various initial dye concentrations.
Dye

C0 (mg/L)

qe(exp)

qe(cal)

k2

r2

Acidic Blue

20
40
60
80

2.52
3.95
5.75
7.62

2.42
3.98
5.76
7.60

0.12399
0.07175
0.06173
0.10742

0.983
0.9997
0.9996
0.9998

Basic Red

20
40
60
80

6.73
12.49
18.85
25.1

7.79
12.69
19.12
25.24

0.00377
0.00611
0.00558
0.00506

0.992
0.993
0.997
0.997

32
65
94
123

1.06
1.51
1.96
2.53

1.05
1.54
2.06
2.55

0.24359
0.07800
0.03278
0.14656

0.992
0.996
0.998
0.9996

Kinetics models
Pseudo-rst order
The pseudo-rst order model due to Lagergren was used in
order to check its probable applicability for the adsorption results
onto the granular coal (Eq. (2)). If the reaction of desorption is

60

Reactive Yellow

K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

Pseudo-second order
The pseudo-second order model (Eq. (3)) was applied to the
three studied systems. Fig. 5 (adsorption of RY) shows a very good
agreement between the extrapolated kinetic values and the
experimental dye removal results, at various initial dye concentrations. The same observation was made in case of the two other
dyes (AB and BR). Therefore, this model is valid for all intervals of
contact time. The different obtained data (initial sorption, pseudosecond order constant, adsorption capacity and linear regression
coefcients) are grouped in Table 4. The adsorption constant values
for each dye were similar; the basic dye had the lowest ones.
Generally, the constant values decrease when the dye concentration increases, except in case of the highest concentration of the
anionic dyes (AB and RY) yielding very high values. The cationic
dye (BR) had a different behavior, and gave a low value for the
2
lowest dye concentration. The initial adsorption rate (h k q2e )
presents some differences between the cationic (BR) and the
anionic dyes (AB and RY): it increases for the rst case when the
concentration increases, but decreases for the second one, while
remaining in the same order for each dye. On the other hand, the
variation of the sorbed amounts of dyes at equilibrium (qe(exp))
were in proportional relationship with the dye concentration. The
regression coefcients (r2  0.99) indicate that the experimental
points are very adjusted to the theoretical model line. On the other
hand, the calculated and experimental data are almost the same.
With the overall pseudo-second order reaction, two elementary
rst-order reactions between adsorbate and free sites, then
between adsobate and solution the two-partial order with respect
to the free sites concentration and the zero-partial order of the
solute in the solution could be assumed. Ho and McKay [40]
indicated that if the dye removal is controlled by a chemical
kinetics, the pseudo-second order constants will not depend on the
particle diameter but in contrast, the stirring velocity will depend
on the concentration of ions in solution.
Elovich equation
The adsorption of the three studied systems was modeled
according to the Elovich equation (Eq. (4)). The three systems were
well modeled by this equation. Fig. 6 gave the example of GAC/AB
system, showing a very good adjustment of the experimental data
on the acid dye removal at various initial dye concentrations.
Table 5 presents the results deduced from the linear plots of qt
versus ln t, where b is a constant related to the extension of
covered surface, and a is in relationship with chemi-sorption rates.

501

Table 5
Elovich model parameters of dye adsorption onto granular activated carbon at
various initial dye concentrations.
C0 (mg/L)

r2

Acidic Blue

20
40
60
80

4.23155
2.90808
3.80315
9.47060

0.28860
0.74206
0.81288
0.22166

0.966
0.948
0.980
0.987

Basic Red

20
40
60
80

0.72836
0.68835
0.45448
0.40262

1.5  101
5.4  102
5.1  106
3.4  1012

0.982
0.966
0.980
0.981

32
65
94
123

2.33628
2.09437
1.84254
1.16818

0.33308
0.38206
0.40334
0.71507

0.988
0.990
0.996
0.987

Reactive Yellow

The two constants were determined from the intercepts and slope
of plots. It was noted that both b values of the used dyes were
similar, and increase with increasing concentration (acid dye),
except for the lowest concentration. Conversely, they decrease
with increasing concentration (basic and reactive dye). Moreover
the extension of the covered surface by anionic dye molecules was
more signicant than that of the cationic dye. The chemi-sorption
rates, indicated by the coefcient a, vary with dye concentration;
the best values were obtained in case of the basic dye. The initial
dye concentration increases with increasing chemi-sorption rate,
except for the highest concentration of the acid dye. From r2 values,
it may be deduced that Elovich model can be accepted as one of
characteristics of the adsorption reaction. Elovich equation,
initially used to express the beginning of sorption process, long
time before equilibrium, can be used correctly in case of chemisorption with highly heterogeneous materials [41]. Several authors
showed that an initial fast adsorption followed by a slow
chemisorption is well expressed by Elovich equation, in particular
when the adsorption process follows the pseudo-second order
[42]. According to each studied system, the phenomenon was
differently explained, by the presence of different nature sites with
different energies on the adsorbent surface, or by the modication
of the nature of the bonding between adsorbate and adsorbent. In
addition, during the adsorption process, the energy state of the still
vacant sites can be modied by a surface contamination.

12
20 mg/L
40 mg/L
60 mg/L
80 mg/L

10

20 mg/L
40 mg/L
60 mg/L
80 mg/L

30

q e (mg/g)

q t (mg/g)

20

10

0
2

ln(t)
Fig. 6. Adjustment of Acidic Blue adsorption to standard Elovich model at various
initial dye concentrations.

12

15

1/2

(t)

Fig. 7. Adjustment of Basic Red adsorption to intra-particle diffusion simple model

at various initial dye concentrations.

K.D. Belaid et al. / Journal of Environmental Chemical Engineering 1 (2013) 496503

502

Table 6
Intra-particle diffusion parameters of dye adsorption onto granular activated
carbon at various initial dye concentrations. V = 1700 mL; m = 3.4 g; stirring = 500 rpm.
C0 (mg/L)
Acidic Blue
20
40
60
80
Basic Red
20
40
60
80

Time (min)

Cst

r2

kid

0300
040
040
040

1.37  0.02
2.23  0.10
4.42  0.05
7.06  0.02

0.05266
0.22012
0.15462
0.06102

0.989
0.958
0.991
0.989

5150
5180
5180
10180

0.21  0.17
6.72  0.16
12.16  0.11
17.22  0.18

0.55701
0.37491
0.44251
051315

0.981
0.976
0.994
0.991

0.02  0.08
0.01  0.04
0.02  0.02
0.01  0.09

0.16337
0.20161
0.24068
0.53546

0.955
0.992
0.999
0.991

Reactive Yellow
32
050
65
040
94
040
123
020

Diffusion models
External diffusion
In order to examine the reliability of the experimental results
with the transfer of dyes from the liquid phase onto the solid phase,
known as external diffusion stage, Eq. (5) was applied for the three
considered systems (GAC/AB, GAC/BR and GAC/RY). It was found
that this model is not suitable to express all the cases studied;
therefore the external diffusion is not a determining stage in the
sorption process. This is probably attributed to the perfect stirring
of mixtures during all the experiments. Although it is agreed that
during the initial stage of adsorption (rst minutes), the
intraparticle resistance is negligible, and the transport of the
aqueous species toward the solid phase is mainly ensured by the
external diffusion mechanism [38], this stage is not determining,
especially if the experimental system is well stirred up [20].
According to the external diffusion equation (Eq. (5)) and the
pseudo-rst order equation (Eq. (2)), it may be easier to notice
their similarity. We might say that because the process does not
follow the pseudo-rst order model, the external diffusion cannot
be the adsorption determining.
Intra-particle diffusion
The experimental data were compared with the intra-particle
diffusion model to check their conformity with Eq. (6). The testing
of the model for the three systems (GAC/AB, GAC/BR and GAC/RY)
shows a good agreement; the linearity extends as of the rst
minutes until the equilibrium, with high correlation coefcients
(r2  0.96). For instance, Fig. 7 presents the application of this
model to GAC/BR system for the used initial dye concentrations
(20, 40, 60 and 80 mg/L). Table 6 expresses the obtained data
corresponding to the linear part of the curve. Kinetic constants for
each dye are similar; the smallest ones were those of BR dye. The
intra-particle diffusion constants generally increase with increasing of the concentration for the two systems: GAC/BR and GAC/RY.
In case of the GAC/AB system, the opposite was observed: when the
concentration increases the constant decreases, except for the
lowest concentration. The initial dye concentration inuences the
process kinetics, and the intra-particle diffusion constant kid varies
proportionally with the dye concentration, except in the case of AB.
Moreover, Eq. (7) appears to be the adequate model to represent
the two GAC/BR and GAC/AB systems, because the intercept of
plots do not pass by zero, but by values which vary proportionally
with the initial dye concentration. The pseudo-second order may
be regarded as the determining adsorption step for these two dyes.

On the other hand, the suitable model to express the reactive dye
adsorption was represented by Eq. (6) since the found values of
constants tend toward zero. From the values of r2, the diffusion of
dyes through the pores of granular carbon seems to be a
determinant stage, controlling the adsorption kinetics of RY dye
adsorption onto GAC. This phenomena was expected because of
the relatively high diameter of coal particles (1 mm < d < 2 mm),
allowing the activated carbon to be a highly porous material. Allen
et al. [43] indicated that the activated carbon, compared with other
sorbents, can have both high surface area of 1100 m2 g1 and
porosity of 47%.

Conclusions
The effect of initial dye concentration of two anionic dyes (AB,
RY) and cationic dye (BR) on adsorption kinetics has been
investigated. The elimination rates of the three dyes slightly
decrease with increasing of the initial dye concentration. However,
the sorption capacities of adsorbed dye per gram of adsorbent for
all sorbent/dye systems increase.
The reactive dye possesses the lowest rate of elimination during
the rst minutes, while the basic dye, being more uid, has been
the most adsorbed dye.
The adsorption process is governed by the pseudo-secondorder reaction, at various initial dye concentrations for the two
dyes BA and BR. Moreover intra-particle diffusion represents a
determinant stage, controlling the adsorption kinetics of dyes the
RY dye onto porous granular activated carbon.
Elovich model describes very well the experimental results,
predicting a chemisorption process of dyes onto different nature
sites of heterogeneous activated carbon.
Acknowledgements
K.D. Belaid and S. Kacha would like to thank the Ministry of
Higher Education and Scientic Research of Algeria for nancial
support.

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