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Microporous and Mesoporous Materials 111 (2008) 228235

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Comparison of textile dyeing euent adsorption on

commercial activated carbon and activated carbon prepared
from olive stone by ZnCl2 activation
a,*
Mehmet Ugurlu , Ahmet Gurses b, Metin Ackyldz b

a
Department of Chemistry, Faculty of Science and Arts, Mugla University, Mugla 48000, Turkey
b
Department of Chemistry, K.K. Education Faculty, Ataturk University, 25240 Erzurum, Turkey

Received 21 May 2007; received in revised form 24 July 2007; accepted 24 July 2007
Available online 1 August 2007

Abstract

Adsorption of Remazol Red B on activated carbon prepared from olive stone and commercial activated carbon from aqueous solutions
was compared. Dierent activating agent (ZnCl2) amounts and adsorbent particle size were studied to optimize adsorbent surface area. The
adsorptive property of commercial activated carbon and activated carbon prepared from olive stone were investigated in terms of adsor-
bent dose, temperature, equilibrium time and pH. Then the obtained results were compared for all parameters, According to the results, the
equilibrium time, optimum pH, adsorbent dosage were found 60 min, pH < 34 and 1.0 g/50 ml respectively. Lower adsorption capacity
for RRB on activated carbon prepared from olive stone was found. The kinetic data for both adsorbents supports pseudo-second order
model (r2 > 0.99) and intra-particle model (r2 > 0.95) but the rst order kinetic model did not adequately t to the experimental values
(r2 < 0.76). The equilibrium adsorption data were interpreted using Langmuir and Freundlich models. The adsorption of Remazol Red
B was better represented by the Langmuir equation. In addition, the thermodynamic parameters, standard free energy (DG), standard
enthalpy (DH), standard entropy (DS) of the adsorption process were calculated for both adsorbents. To reveal the adsorptive charac-
teristics of the produced active carbon, surface area measurements were carried out and structural analysis was performed using SEM-
EDS.
 2007 Elsevier Inc. All rights reserved.

Keywords: Adsorption; Chemical activation; Olive stone; Kinetic equations; Textile dyeing euent

1. Introduction The treatment of dyes in industrial wastewater possesses

The introduction of waste products to the environment
is a world wide problem that has been highlighted by var-
ious environmentalist groups. Colored organic euents are
produced in industries such as textiles, rubber, paper, plas-
tic, cosmetics, etc. Discharging of dyes into water resources
even in a small amount can aect the aquatic life and food
web. Dyes can also cause allergic dermatitis and skin irrita-
tion. Some of them have been reported to be carcinogenic
and mutagenic for aquatic organisms.
*
Corresponding author. Fax: +90 2522238656.
E-mail address: mnazlican@hotmail.com (M. Ugurlu).
several problems since dyes are generally dicult to biode-
gradate and photodegradate. Many dierent techniques
including cloud point extraction, oxidation processes, nano-
ltration, ozonation and coagulation have been used for the
removal of colored dyes from wastewater [16]. However,
adsorption is the most popular physicochemical treatment
for the removal of dissolved organics from waters.
Activated carbon has been the water industrys standard
adsorbent for the reclamation of municipal and industrial
wastewater for potable use for almost three decades. Acti-
vated carbons have the advantage of exhibiting a high
adsorption capacity for organic pollutants due to their high
specic surface area, adequate pore size distribution, and
relatively high mechanical strength [79].

1387-1811/$ - see front matter  2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.07.034
 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235
There are quite a large number of studies regarding the
preparation of activated carbons from agricultural wastes
[10,11], such as nutshells [12], fruit stones [13], bagasse
[14], oil palm waste [15] and agricultural residues from sug-
arcane [16], peanut [17], sawdust [18], Rosa canina sp seeds
[19] and canes from some easy-growing wood species [20].
Basically, there are two dierent processes for the prepara-
tion of activated carbon: physical activation and chemical
activation. In comparison with physical activation, chemi-
cal activation has two important advantages. One of them
is the lower temperature in which the process is accom-
plished. The other is that the global yield of the chemical
activation tends to be greater since burn-o char is not
required. Among the numerous dehydrating agents, zinc
chloride in particular is the widely used chemical agent in
the preparation of activated carbon [21]. Knowledge of dif-
ferent variables during the activation process is very impor-
tant in developing the porosity of carbon sought for a given
application. Chemical activation by ZnCl2 improves the
pore development in the carbon structure [6,12,2225].
Turkey is one of the Mediterranean countries on which
olive is grown and produces olive oil. The annual produc-
tion of olive oil in Turkey is between 100,000 and
250,000 tons. This generates signicant amount of solid
wastes [25].
In this study, olive stone (pirina in Turkish and Greece)
from olive oil industry in Mugla region in Turkey has been
used for preparing activated carbon. Optimization of some
process parameters and characterization of prepared acti-
vated carbon were investigated. In addition, it was aimed
to compare the adsorption ability of Reactive Red 22, by
the prepared active carbon from olive stone (ACOS) and
commercial activated carbon (AC). To determine the t-
ness of adsorption data to the dierent kinetic models
and the adsorption isotherms, Langmuir and Freundlich,
some thermodynamic parameters, such as Gibbs free
energy (DG), isosteric adsorption enthalpy (DHs), isoster-
ic adsorption entropy (DS) were calculated for both
adsorbents.
2. Material and methods
2.1. Preparation and characterization of activated carbon
Olive stone samples used for producing activated carbon
were taken from olive oil factories in Mugla region in Tur-
key. The samples were washed with water to remove dirt
and other contaminants and oven-dried at about 110 C
for 24 h. Then, 40 g samples of stone were rstly crushed
with hammer and then grounded using a mill to obtain a
suitable particle size and dried at 110 C for 24 h. Finally,
oil in olive stone was removed with hexane extraction
method by using a Soxholet Apparatus.
Pyrolysis experiments were carried out in a xed bed
reactor. The system consists of a mue furnace connected
to a packed column, sample holder, a temperature control
unit and some necessary facilities. The sample holder, made
229
from stainless steel with 3.0 cm inner diameter and 14.0 cm
length having a sample room placed into middle of porce-
lain furnace, which was heated by an electrical power. The
temperature was measured and controlled in the middle of
the porcelain furnace and in the raw sample by a two Ni
Cr thermocouple. The furnace is safely held at desired tem-
perature by this controlling system. To maintain inert
atmosphere, highly pure N2 gas (>99.99 %) was charged
to the furnace at the ow rate of 2100 mL min1 during
the activation process. All chemicals used in this study were
obtained from Merck.
2.2. Activation procedure
The general procedure of the activation process is
described with a few modications as below [6,7,12].
1. Impregnation was carried out about 70 C in a water
bath until the excess water was evaporated. The samples
were taken to oven-dried at 120 C for 24 h.
2. Olive stone samples were mixed with 200 ml of the aque-
ous solutions of 10%, 20% and 30% ZnCl2 (w/w).
3. The samples of impregnated olive stone were placed at
the centre of a stainless steel tubular reactor. This reactor
was placed horizontally in side the mue furnace. The
activation temperature was set at 650 C under an inert
ow N2 gas (150 cm3 min1 STP) for 2 h carbonization.
4. The products were washed sequentially with 0.5 N HCl,
hot water and nally cold distilled water to remove
residual organic and mineral matters.
5. The samples were then vacuum-dried at 102 C. A nal
product yield or loss due to washing process was
recorded. The nal product was stored in a desiccators
lled with N2 gas to prevent oxidation. In all experi-
ments, carbonization temperature (650 C) and N2 ow
(150 cm3 min1 STP) were kept constant.
The activated carbons were weighed to determine acti-
vation burn-o or mass loss due to activation and calcu-
lated by the following equation [19]:
Activation burn-off %
  
mass after activation g
100   100 1
original mass g
The BET surface areas of prepared activated carbons were
calculated from N2 adsorption by using the BrunauerEm-
mettTeller (BET) method with Micrometritics model,
Flowsorb II-2300 adsorption meter. SEM photographs
were recorded without sample coating by Philips XL-30S
FEG model scanning electron microscope. Chemical com-
positions of produced activated carbons were analysed
with EDX detector of SEM. The various physico-chemical
characteristics of the activated carbon prepared from olive
stone is given in Table 1.
It can be seen from Table 1 that surface area of the acti-
vated carbons is highly depend on the amount of the acti-
230 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235

Table 1
Physico-chemical and other properties of activated carbon from olive stone
ACOS Impregnation solution Particle size Weight loss BET surface Chem. comp. (%)
Sample no. by ZnCl2 (w/w %) (lm) (%) area (m2/g)
C O S
ACOS 0.0 350> 40.02 3 64.4 34.0 0.5
ACOS1 10 350P 47.24 58 86.1 13.1 0.4
ACOS2 20 350> 45.21 790 90.1 9.5 0.3
ACOS3 30 350< 51.45 167 87.3 11.7 0.1
ACOS4 20 350< 48.13 108 89.1 10.2 0.6
ACOS5 20 150< 47.41 506 88.1 10.9 0.9
ACOS6 25 350< 47.89 638 89.9 9.1 0.9
ACOS7 15 150< 48.12 553 89.7 9.3 0.9

vation agent and particle size. The surface area of the
resulting activated carbons is maximum with 20% ZnCl2
solution. The BET surface area of ACOS2 is 790 m2/g.
2.3. SEM analysis of the activated carbons
activated carbon, probably due to the presence of remain-
ing zinc chloride or other metal compounds on the acti-
vated carbon. Some particles were even trapped into the
pores and could possibly block the entry of pores to some
extent.

Scanning electron microscopy (SEM) technique was 2.4. Adsorption experiments

employed to observe the surface physical morphology of
the olive stone derived activated carbon. Fig. 1 shows the
SEM photographs of the olive stone before and after the
carbonization at the optimum operating condition with
1000 magnication. It can be seen from the micrographs
that the external surface of the chemically activated carbon
is full of cavities, exhibiting a heterogeneous structure in
terms of both size and shape. The reason for the formation
of the cavities on the ZnCl2 activated carbon is not clear.
According to this micrograph, it seems that the cavities
resulted from the evaporation of ZnCl2 during carboniza-
tion, leaving the space previously occupied by the ZnCl2.
The carbonization temperature for chemical activation
was too low to cause the agglomeration of the char struc-
ture. Since the carbonization temperature for physical acti-
vation is high (900 C), caking and agglomeration occurred
on the char structure and thus resulted in the formation of
chars with an intact external surface. It can also be said
that some salt particles are scattered on the surface of the
Because of the largest specic surface area, the perfor-
mance of produced active carbon with 20% ZnCl2 (ACOS2)
and commercial active carbon (AC) obtained from Carlo
Erba (specic surface area: 1435 m2/g, Code no: 434454)
were compared in the adsorption experiments. The dye
used in the study is Remazol Red B (C.I. Reactive Red
22 (RR 22), 14282), 2-(3-amino-4-methoxy phenyl sulpho-
nyl) ethanol sulphate ester!1-naphthyl-5-sulphonic acid,
widely used in dyeing cotton and obtained from Boysan
textile industry in the Marmara region of Turkey. Its struc-
ture is given in Fig. 2.
The experimental parameters for all experiments were
selected as contact time, initial pH, adsorbent dosage and
temperature. Batch adsorption experiments were con-
ducted in a shaker batch at 15, 25, and 35 C constant.
The dye solutions at the dierent concentrations were pre-
pared by diluting a stock solution of the dye. The pH
adjustments were done using concentrated HCl and NaOH

Fig. 1. SEMs of (a) ACOS2, activated carbon (b) raw olive stone.
 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235
Fig. 2. The structure of Remazol Red B (RRB).
solutions. The concentration of dye remaining in the super-
natant after and before adsorption was determined with a
spectrophotometer (Shimadzu UV1201) at kmax of
540 nm. The amount of dye adsorbed was calculated from
the concentrations in solution before and after the adsorp-
tion. The calibration curve was plotted from the dye solu-
tions prepared in the concentration of 1100 mg/L.
Samples (0.25 g) of adsorbents were added to each 50 ml
volume of dye solution separately.
3. Result and discussion
3.1. Eect of contact time
The relationships between contact time, color removal
and amount adsorbed by ACOS and AC are presented in
Fig. 3. It can be seen from the gure that the percentage
of removal of AC were higher than that of ACOS and
the adsorption of dye onto AC and ACOS increases when
increasing treatment time starting from 0 to 30 min, and
then becomes constant around 40 min. The adsorption pro-
cesses reach equilibrium at about 60 min for both adsor-
bents. Maximum removal for AC and ACOS were
respectively observed 80% and 60%. This dierence
Fig. 3. The eect of contact time on the adsorption of textile dyeing
euent (initial conc.: 10 mg/L. T: 298 K. pH: 7.0 and solid/liquid ration:
0.25 g/50 mL).
231
Fig. 4. The eect of adsorbents dosage on the adsorption of textile dyeing
euent (initial conc.: 10 mg/L. T: 298 K. pH: 7.0 and contact time:
60 min).
between the maximum removal percents can be attributed
to the higher specic surface area of AC.
3.2. Eect of adsorbent dosage
The eects of adsorbent dosage on the removal percent-
age and adsorbed amount per mg/g of adsorbent have been
presented in Fig. 4. While sorbent dosage increases from
0.25 g/200 ml to 1.2 g/200 ml at 60 min adsorption time,
the adsorption capacity of dye onto AC and ACOS carbon
changes from 60% and 50% to 90% and 75%, respectively.
Therefore, it can be said that an increase in sorbent dosage
leads to an increase in the adsorption capacity and then
become almost constant between 1.0 and 1.2 g/200 ml. It
is apparent that the percent removal of color in the exper-
iments due to the greater availability of the exchangeable
sites and surface areas at higher concentrations of the
adsorbent. In addition, increasing the adsorbent dosage
at a xed dye concentration provided more available
adsorption sites for dye and thus increased the extent of
dye removal [26,27].
3.3. Eect of pH
The variation of dye adsorption onto ACOS and AC
with adsorption time was investigated as a function of ini-
tial suspension pH in the range of pH 312 and the results
are given in Fig. 5. This gure depicts that color removal
percentage and adsorbed amounts decreases with increas-
ing pH. This can be explained by considering the surface
change on the adsorbent material. The adsorption of dye
from aqueous solution onto activated carbon surface is
highly dependent on pH of the solution which aects both
surface functional groups and topography of the sorbent
and dye structure [6,21]. Increase of adsorption under
acidic conditions may be related to preference of the dye
cations for active sites and/or the increasing of accessibility
232 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235

Fig. 5. The eect of initial pH on the adsorption of textile dyeing euent

(initial conc.: 10 mg/L. T: contact time: 60 min and solid/liquid ration:
0.25 g/50 mL). Fig. 6. Kinetic of dye removal according to pseudo-second-order model
(initial conc.: 10 mg/L. T: pH: 7.0 and solid/liquid ration: 0.25 g/50 mL).
to interlayer regions of protonated and monomeric species
[6].

3.4. Kinetics of adsorption

The mechanism of adsorption depends on the physical

and/or chemical characteristics of the adsorbent as well
as on the mass transport process. In order to investigate
the mechanism of adsorption, the pseudo-rst-order kinet-
ics model, the pseudo-second-order kinetics model and the
intra-particle diusion model were used to test dynamical
experimental data. These mechanisms are described shortly
as follows [2831]:
Pseudo-rst-order model:
K ads
log qe  qt log qe  t 2
2; 303
Pseudo-second-order model:
Fig. 7. Kinetic of dye removal according to intra-particle diusion model
t 1 1 (initial conc.: 10 mg/L. T: pH: 7.0 and solid/liquid ration: 0.25 g/50 mL).
t 3
qt k 2 q2e qe
Intra-particle diusion model: the pseudo-second order model and Intra-particle diusion
are given in Table 2.
qt k d t0:5 c 4
The linearity of these plots indicates that r2 value of the
where qt is the amount of dye adsorbed (mg/g) at time t pseudo-second-order model (r2: 0.999; an indication of a
(min), qe the amount of dye adsorbed at equilibrium (mg/g) chemisorption mechanism) ts better than that of the
and Kads is the equilibrium rate constant of pseudo-rst- pseudo-rst-order model (r2 < 0.76). Moreover, for the sec-
order adsorption (min1). In addition, k2 and kd are the ond-order model, qe.calc, values are close to qe.exp for both
pseudo-second-order rate constant of adsorption and the adsorbents (Table 2).
rate constant of intra-particle diusion (mg/g min1/2) respec- The intra-particle diusion model may present multi-lin-
tively (Figs. 6 and 7). earity, indicating that a few steps take place. The rst, shar-
It was found that the rst-order kinetic model did not per portion is attributed to the diusion of adsorbate
adequately t to the experimental values. Therefore, only, through the solution to the external surface of adsorbent
r2 values are given in Table 2. In contrast, the pseudo-sec- or the boundary layer diusion of solute molecules. The
ond order rate equation for the sorption of dye euents second portion describes the gradual adsorption stage,
onto AC and ACOS tted well with the data. The correla- where intra-particle diusion rate is rate-limiting. The third
tion coecients and the other parameters calculated from portion refers to the nal equilibrium stage for which the
 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235 233

Table 2
First and pseudo-second order kinetics and intra-particle diusion model parameters for the adsorption systems in the study
Adsorbents First-order Pseudo-second-order Intra-particle
model model diusion
r2 qe,exp qe,calc k2 r2 k1 r2 k2 r2 k3 r2
(mg/g) (mg/g) (g/mg min) (mg/g min1/2) (mg/g min1/2) (mg/g min1/2)
AC 0.746 1.66 1.659 2.441 0.999 0.329 0.998 0.0453 0.974 0.0044 0.892
ACOS 0.756 1.25 1.246 1.833 0.999 0.209 0.966 0.0312 0.998 0.0048 0.867

intra-particle diusion starts to slow down due to the extre-
mely low adsorbate concentration left in the solution
[27,3234]. The rate of uptake might be limited by the size
of adsorbate molecule, concentration of the adsorbate and
its anity to the adsorbent, diusion coecient of the
adsorbate in the bulk phase, the pore size distribution of
the adsorbent, and degree of mixing. The intra-particle dif-
fusion is the generally rate-limiting step for the systems
with high concentration of the adsorbate, good mixing,
large particle size of adsorbent and low anity towards
adsorbent [14,34].
Fig. 7 shows the plots of fractional uptake for RRB
(Reactive Red B) versus square root time on AC and
ACOS. As seen the plots are not linear over the whole time
range, implying that more than one process aects the RRB
adsorption. The multiple natures of these plots can be
explained in terms of few processes, i.e., boundary layer dif-
fusion which gives the initial part of the plot and the intra-
particle diusion which gives further the two linear parts. If
the intra-particle diusion is the only rate-controlling step
then the plot passes through the origin, if not, the boundary
layer diusion aects the adsorption to some extent [35]. As
can be seen in Fig. 7, for AC and ACOS, the intra-particle
diusion is likely to occur in three stages. The adsorbate
molecule rapidly enters macropores and wider mesopores
and then penetrates more slowly into smaller mesopores.
From this gure, the linear portion of the plot for a wide
range of contact time between adsorbent and adsorbate
does not pass through the origin. This deviation from the
origin or near saturation may be perhaps due to the dier-
ence in the rate of mass transfer in the initial and nal stages
of adsorption. Further, such deviation from origin indicates
that the pore diusion is not the only rate controlling step
[12,36]. If intra-particle diusion rate constants are com-
pared for both adsorbents, it is easy to see that k1 (rst
stage) > k2 (second stage) > k3 (third stage). As a result,
the intra-particle diusion model and pseudo-second kinetic
models are applicable with AC, ACOS for RRB adsorption.
The applicability of both models showed that sorption pro-
cess is complex and involves more than one mechanism.
3.5. Adsorption isotherms
In this work, Langmuir and Freundlich isotherm models
were used to describe the relationship between the amount
of dye adsorbed and its equilibrium concentration in solu-
tion for three temperatures (288 K, 298 K, and 308 K) for
2 h (see Figs. 8 and 9).

Fig. 8. Langmuir adsorption isotherms of dye removal onto ACOS (a) and AC (b) at dierent temperatures.
234 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235

Fig. 9. Freundlich adsorption isotherms of dye removal onto ACOS (a) and AC (b) at dierent temperatures.

The linear form of the Langmuir isotherm model can be Table 3

represented by using the equation Parameters of dierent adsorption models at various adsorbents and
   temperatures
1 1 1 1
5 Isotherm models Temperature (K)
q qm b  qm Ce
288 298 308
The linear form of the Freundlich isotherm model is Langmuir
given by the following equation: AC qm (mg/g) 6.73 144.92 102.04
b (1/mg) 0.0954 0.059 0.012
1 r2 0.99 0.98 0.98
log qe log K F log C e 6
n ACOS qm (mg/g) 7.28 8.53 9.33
where, Ce; equilibrium concentration (mg L1), q; Amount b (1/mg) 0.294 0.3447 0.350
adsorbed per unit weight of carbon(mg g1); KF = Freund- r2 0.98 0.98 0.99
lich constant (adsorption intensity); 1/n = The order of
Freundlich
adsorption; qm; the maximum adsorption capacity (mg g1); AC KF (dm3/g) 0.072 0.085 0.042
qe; equilibrium amount adsorbed (mg g1); b; Langmuir n 0.229 0.236 0.192
constant related to the energy or net enthalpy of adsorption. r2 0.94 0.83 0.84
The tness of adsorption data to these isotherm equa- ACOS KF (dm3/g) 1.021 1.1926 1.078
tions were checked by carrying out correlation analysis n 0.194 0.202 0.186
between the values of (i) 1/q and 1/Ce, (ii) log q and log Ce r2 0.97 0.97 0.98
for AC and ACOS. The adsorption isotherm parameters
(constants) along with the r2 values (correlation coecients)
are given in Table 3. As can be seen from the isotherms and tion, (DH), isosteric entropy of adsorption (DS), and free
regression coecients, the tness with Langmuir isotherm energy of adsorption (DG) can be calculated by means of
model is better than Freundlich (r2 = 0.992). The Langmuir the following equations [6,9] and represented in Table 4:
parameters, i.e., qm and b, increased with increasing temper- . 1 1

o
ature. It can be concluded that temperature can increase the DH Rln C 2  ln C 1  7
T1 T2
kinetic energy of the dye molecules and, hence, enhanced 
the mobility of the dye ions. DS o Rln C 2  ln C 1 ln T 2  ln T 1 8
o
DG RT ln K c 9
3.6. Thermodynamic study
C, T, and K in the equations represent the equilibrium dye
The thermodynamic parameters including change in the concentrations in dierent temperatures, the absolute tem-
Gibbs free energy (DG) from the adsorption isotherms at perature, and the adsorption equilibrium constant, respec-
three dierent temperatures, isosteric enthalpy of adsorp- tively. The obtained thermodynamic values were given in
 M. Ugurlu et al. / Microporous and Mesoporous Materials 111 (2008) 228235 235

Table 4 [2] S. Chakraborty, M.K. Purkait, S. DasGupta, S. De, J.K. Basu, Sep.
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Adsorbents Temperature DG DH DS 151159.
[4] M. Neamtu, A. Yediler, I. Siminiceanu, M. Macoveanu, A. Kellrup,
(K) (KJ/mol) (KJ/mol) (J/mol K)
Dyes Pigm. 60 (2004) 6168.
AC 288 7.936 3.412 9.099 [5] F. Zhang, A. Yediler, X. Liang, A. Kettrup, Dyes Pigm. 60 (2004)
298 9.911 6.198 8.059 17.
308 9.321 [6] M. Ugurlu, A. Gurses, C . Dogar, Color Technol. 123 (2007) 106114.
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