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1
q
1
k
1
q
1
1
t
where q
1
and q
t
are the amounts of the dye adsorbed at
equilibrium and at time t, in mg g
1
, and k
1
is the rst-or-
der rate constant (min
1
). Values of k
1
from the slope of
the plots of 1/q
t
versus 1/t (Fig. 2) are given in Table 4.
The pseudo-second-order kinetic model (Ho and
McKay, 1998) is expressed as:
t
q
t
1
k
2
q
2
2
1
q
2
t
where q
2
is the maximum adsorption capacity (mg g
1
) for
the pseudo-second-order adsorption, k
2
is the equilibrium
rate constant for the pseudo-second-order adsorption
(g mg
1
min
1
). Values of k
2
and q
2
were calculated from
the plot of t/q
t
against t (Fig. 3). The kinetic data for the
adsorption of methylene blue onto the activated carbons
under various conditions were calculated from the related
plots and are summarized in Table 4.
The intraparticle diusion (Crank, 1933) can be written
by following equation:
q
t
k
p
t
1=2
C
where C is the intercept and k
p
is the intraparticle diusion
rate constant (mg g
1
min
1/2
). According to this model,
the plot of the uptake, q
t
, versus the square-root of time,
t
1/2
is linear. If intraparticle diusion is involved in the
adsorption process and if the line passes through the origin,
the intraparticle diusion is the rate-controlling step (Kan-
nan and Sundaram, 2001; Bhattacharyya and Sharma,
2004; Chen et al., 2003). As can be seen from Fig. 4,
AC1 and AC2 are consistent with intraparticle diusion
but AC3 is not. Table 4 shows the correlation coecients
r
2
p
for the intraparticle diusion model are also lower
than the pseudo-second-order kinetic model. Similar re-
sults have been reported in a previous study which con-
cerned the production of the activated carbon from
Euphorbia Rigida by H
2
SO
4
activation (Gercel et al., 2007).
3.7. Adsorption isotherms
The adsorption data were analyzed with help of the fol-
lowing linear forms of Langmuir and Freundlich isotherms
(Adamson, 1960).
Langmuir isotherm:
C
e
q
e
1
q
max
K
L
C
e
q
max
where q
e
is the equilibrium MB concentration on the acti-
vated carbon (mg g
1
), C
e
is the equilibrium MB concen-
tration in the solution (mg L
1
), q
max
is the monolayer
adsorption capacity of the activated carbon (mg g
1
), K
L
is the Langmuir adsorption constant (L mg
1
).
The plots of C
e
/q
e
versus C
e
for the adsorption of
methylene blue onto the activated carbons are shown in
Fig. 5.
Freundlich isotherm:
log q
e
log K
F
1
n
log C
e
where q
e
is the equilibrium MB concentration on the acti-
vated carbon (mg g
1
), C
e
is the equilibrium MB concen-
tration in the solution (mg L
1
), K
F
(L g
1
) and n are the
Freundlich adsorption isotherm constants. The plots of
log q
e
versus log C
e
for the adsorption of methylene blue
onto the activated carbons are shown in Fig. 6. The Fre-
undlich isotherm endorses the heterogeneity of the surface
and assumes that the adsorption occurs at sites with dier-
ent energy of adsorption. The Langmuir and Freundlich
isotherm parameters for the MB adsorption of the acti-
vated carbons are given in Table 5. The results indicate that
the Langmuir isotherm ts better than the Freundlich iso-
therm. Thus according to a linear regression method, the
0
2
4
6
8
0 10 20 30
t
0.5
(min
0.5
)
q
t
(
m
g
g
-
1
)
AC1
AC2
AC3
Fig. 4. Intraparticle diusion plot for the adsorption of methylene blue
onto the activated carbons.
0
10
20
30
0 50 100 150 200 250
C
e
(mg L
-1
)
C
e
/
q
e
(
g
L
-
1
)
AC1
AC2
AC3
Fig. 5. Langmuir plots for the adsorption of methylene blue onto the
activated carbons.
S. Karago z et al. / Bioresource Technology 99 (2008) 62146222 6219
dye uptake is due to monolayer coverage of solute particles
onto the surface of the activated carbon.
A Langmuir isotherm assumes monolayer adsorption
onto a surface containing a nite number of adsorption
sites of uniform strategies of adsorption with no transmi-
gration of adsorbate in the plane of surface (Adamson,
1960). While a Freundlich isotherm model assumes hetero-
geneous surface energies, in which the energy term in the
Langmuir equation varies as a function of the surface cov-
erage (Adamson, 1960). Table 6 is presented to provide a
comparison for the maximum monolayer adsorption
capacities of the activated carbons from dierent biomass
sources. The maximum monolayer adsorption capacities
of some of the activated carbons were lower (Aygun
et al., 2003) and some of them were higher (Gercel et al.,
2007; Attia et al., 2003) than those in the present work.
Essential characteristics of the Langmuir isotherms can
be described by a separation factor (R
L
) which is dened
by the following equation (Weber and Chakravorti, 1974):
R
L
1
1 K
L
C
o
where C
o
is the initial concentration of MB (mg L
1
) and
K
L
is the Langmuir adsorption constant (L mg
1
). The
value of separation factor (R
L
) indicates the nature of
the absorption process (Kannan and Sundaram, 2001).
In the present study, the values of separation factor (R
L
)
were in the range of 01. This indicates that the adsorption
process of MB is favorable for all activated carbons
prepared.
3.8. Adsorption thermodynamics
Table 7 shows thermodynamic parameters (DG, DH,
DS) for the adsorption process. The Gibbs free energy
change (DG) indicates the degree of the spontaneity of
the adsorption process. The Gibbs free energy changes
(DG) of adsorption must be negative for a better adsorp-
tion. The values of Gibbs free energy change (DG) of
MB adsorption at the temperature of 298.15 K were deter-
mined as +2.22, 0.62, 0.574 kJ mol
1
for AC1, AC2
and AC3, respectively. These values indicate that the
adsorption process led to a decrease in Gibbs free energy
at 298.15 K for AC2 and AC3 whereas it increased in
Gibbs free energy for AC1. The negative value of DH
suggests the exothermic nature of adsorption for the acti-
vated carbons. Plot of ln K
L
versus 1/T for estimation of
thermodynamic parameters for the adsorption of MB onto
(AC1, AC2 and AC3) is shown in Fig. 7.
Thermodynamic parameters including Gibbs free energy
change (DG), enthalpy change (DH) and entropy change
(DS) were calculated from the following equations;
DG
RT ln K
L
where R is the universal gas constant (8.314 J/mol K), T is
the temperature (K) and K
L
value was calculated using the
following equations:
K
L
q
e
C
e
-1
-0.5
0
0.5
1
1.5
-2 -1 0 1 2 3
log C
e
l
o
g
q
e
AC1 AC2 AC3
Fig. 6. Freundlich plots for the adsorption of methylene blue onto the
activated carbons.
Table 5
Adsorption isotherms constants for the adsorption of methylene blue onto
the activated carbons at 25 C
Type of the activated carbon AC1 AC2 AC3
Langmuir
q
max
(mg g
1
) 10.21 16.43 15.798
K
L
(L mg
1
) 0.337 1.150 0.886
R
L
0.548 0.364 0.418
r
2
L
0.9940 0.9926 0.9915
Freundlich
n 2.217 4.425 2.793
K
F
(L g
1
) 0.917 4.300 2.418
r
2
F
0.965 0.838 0.916
Table 6
Comparison of the maximum monolayer adsorption of MB onto activated carbons from various sources
Activated carbon Maximum monolayer
adsorption capacity (mg g
1
)
References
Activated carbon from Almond shell 1.33 Aygun et al., 2003
Activated carbon from Walnut shell 3.53 Aygun et al., 2003
Activated carbon from Hazelnut shell 8.82 Aygun et al., 2003
Activated carbon from Apricot stones 4.11 Aygun et al., 2003
Activated carbon from Euphorbia rigida 114.45 Gercel et al., 2007
Activated carbon from Pistachio shells 129 Attia et al., 2003
Activated carbon from Sunower oil cake 16.43 Present work
6220 S. Karago z et al. / Bioresource Technology 99 (2008) 62146222
where q
e
and C
e
are the equilibrium concentration of MB
ions on the activated carbon(mg g
1
) and in the solution
(mg L
1
), respectively.
The enthalpy change (DH) and entropy change (DS) of
the adsorption were estimated from the following equation:
ln K
L
DS
R
DH
RT
The enthalpy (DH) and entropy (DS) can be obtained
from the slope and intercept of a Vant Ho equation of
(DG) versus:
DG
DH
TDS