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m
o
100 4
m
C
e
V
0
and m
o
C
o
C
e
V 5
where, m
o
(mg) is the mass of dye previously sorbed onto the
adsorbent, m
1
q
m
1
K
L
q
m
1
C
e
7
Fig. 4 Effect of adsorbent dosage on the removal of CR by SD and
CTAB/SD (initial dye concentration = 100 mg L
1
and contact
time = 60 min)
Fig. 5 Effect of initial dye concentration on the adsorption capacity
of SD and CTAB/SD (adsorbent dosage = 0.80 g and contact
time = 60 min)
Fig. 6 Effect of contact time on the removal of CR by SD and
CTAB/SD (initial dye concentration = 100 mg L
1
and adsorbent
dosage = 0.80 g)
J Surfact Deterg (2012) 15:557565 561
1 3
Where, q
m
is the maximum amount of adsorption which
complete monolayer coverage on the adsorbent surface
(mg g
-1
) and is related to the surface area of adsorbent, K
L
is the Langmuir constant (L mg
-1
) which implies
adsorption enthalpy and its value depends on the nature
of adsorbate and the adsorbent surface. The Langmuir
constants K
L
and q
m
can be determined from the linear plot
of 1/C
e
versus 1/q
e
or C
e
/q
e
versus C
e
. According to Hall
et al. [29] the favorable adsorption of the Langmuir
isotherm can be expressed in terms of a dimensionless
constant separation factor or equilibrium parameter R
L
.
R
L
1
1 K
L
C
i
8
where, C
i
is the maximum initial CR concentration
(mg L
-1
). The values of this parameter are basically
classied into four groups, indicating the shape of the
isotherm, in which R
L
[1 is unfavorable, R
L
= 1 is linear,
0 \R
L
\1 is favorable, and R
L
= 0 is irreversible.
Freundlich [30] presented the earliest known sorption
isotherm equation. This empirical model can be applied to
non-ideal sorption on heterogeneous surfaces as well as
multilayer sorption and is expressed by the following
equation,
q
e
K
F
C
1=n
e
9
Equation 9 can be subsequently linearized by taking
logarithms:
log q
e
log K
F
1
n
log C
e
10
where, q
e
is the amount of dye adsorbed per unit of
adsorbent (mg g
-1
), C
e
is the concentration of dye solution
at adsorption equilibrium (mg L
-1
), K
F
(mg
1-1/n
g
-1
L
1/n
)
and n (dimensionless parameter) are the empirical Fre-
undlich adsorption isotherm constants relating to the
adsorption capacity and adsorption intensity respectively. It
is generally assumed that systems obey this equation and
that adsorption results in a multilayer instead of a single
monolayer. The favorable adsorption of this model can be
characterized such that if a value for n is above unity,
adsorption is favorable and a physical process [2]. The
magnitude of the Freundlich constant n gives a measure of
favorability of adsorption. The values of n between 1 and
10 (i.e., 1/n \1) represents a favorable sorption. The
Freundlich isotherm is linear if 1/n = 1 and, as 1/
n decreases, the isotherm becomes more nonlinear [31].
The calculated constants for the above mentioned models
together with correlation coefcients have been summa-
rized in Table 1.
As the obtained isotherm parameters show (Table 1),
CTAB/SD has a high adsorption capacity for anionic CR
dye in the solution. This shows that modication of saw-
dust by CTAB greatly improves its sorption properties
toward CR dye. It can also be seen that for CTAB/CD, the
Freundlich model yields a much better t than the Lang-
muir model. This, however, is indicative of the heteroge-
neity of the adsorption sites on the CTAB/SD particles and
multilayer adsorption than monolayer predicted by the
Langmuir equation. But for SD, the experimental results
indicate that sorption of CR onto SD follows the Langmuir
model. A good t of the Langmuir isotherm to the exper-
imental data for SD conrms that the adsorption is
monolayer. The R
L
values for the adsorption of CR onto
adsorbents are 0 \R
L
\1 also shows that the adsorption
process for both SD and CTAB/SD is favorable.
Fixed Bed Column Experiments, Breakthrough
Curve Analysis
Effect of pH
The breakthrough curves are obtained from the plot of
C
t
/C
0
versus efuent volume (V
eff
) in continuous or ow
systems. The breakthrough curves for CTAB/SD obtained
at different pH values are shown in Fig. 7. As the results
show, maximum dye removal occurred at pH of 6.0 for
CTAB/SD adsorbent. As we have already shown, the same
optimal pH value was observed in batch system for CTAB/
SD. The breakpoint observed in the breakthrough curve
occurred after passing about 750 mL of the dye solution.
Instead, the breakpoint for unmodied SD happened very
quickly (V
b
* 20 mL). On the other hand, modication of
sawdust with cationic surfactant (CTAB) improved its
sorption capacity toward CR anionic dye more than
35 times. A great enhancement in sorption capacity of SD
is resulted upon its simple modication CTAB surfactant.
Electrostatic interaction between the positive charged
introduced by cationic surfactant (CTAB) on the surface of
modied sawdust and the negatively charged CR dye
Table 1 Isotherm constants for the adsorption of CR on SD and CTAB/SD
Adsorbent Langmuir constants Freundlich constants
q
m
(mg g
-1
) K
L
(L mg
-1
) R
L
R
2
K
F
n R
2
SD 5.18 0.052 0.0877 0.9867 1.03 3.18 0.9040
CTAB/SD 9.07 16.71 0.0003 0.9418 8.10 3.94 0.9876
562 J Surfact Deterg (2012) 15:557565
1 3
molecules, can be considered as the main reason for the
improved sorption capacity of the CTAB/SD adsorbent.
Due to the fast happening of breakpoint and negligible
sorption capacity of SD for CR dye sorption, the further
column studies was carried out only for CTAB/SD
adsorbent.
Effect of Inuent Dye Concentration
on the Breakthrough Curve of CTAB/SD
The effect of inuent CR concentration on the shape of the
breakthrough curves is shown in Fig. 8. As shown in
Fig. 8, the break point of the curve begins after the passage
of about 1,600, 700 and 180 mL of the CR solution for
CTAB/SD when inuent concentration was 20, 50 and
100 mg L
-1
, respectively. It is illustrated that the break
point of the curve decreased with increasing inuent CR
concentration. As inuent concentration increased, sharper
breakthrough curves were obtained. This can be explained
by the fact that a lower concentration gradient caused a
slower transport due to a decrease in the diffusion coef-
cient or mass transfer coefcient. With increasing of the
inuent concentration, the steeper is the slope of break-
through curve and the break point of the curve occurred
more quickly. These results demonstrate that the change of
concentration gradient affects the saturation rate and break
point of the curve, which implies that the diffusion process
is concentration dependent.
Effect of Flow Rate and Bed Depth
on the Breakthrough Curve of CTAB/SD
To investigate the effect of ow rate, the breakthrough
curves at different ow rates (3.012.0 mL min
-1
) were
plotted while the other conditions such as inuent dye
concentration, sorbent dosage and pH were held constant.
For investigation of the effect of bed height, the
breakthrough curves at different bed depths (2.510.5 cm)
were plotted at constant inuent concentration (C
0
= 50
mg L
-1
), and ow rate (v = 3.0 mL min
-1
). The data
obtained from the related breakthrough curves (Supple-
mentary material 1) as well as initial inuent concentration
have been summarized in Table 2.
As the results show (Table 2), the breakpoint generally
occurred faster at higher ow rates. The breakpoint of the
curve reaching saturation also increased signicantly with
a decrease in the ow rate. When, at a low rate of inuent,
CR had more time to contact with CTAB/SD that resulted
in higher removal of CR ions in column. The reason is that
at a higher ow rate the rate of mass transfer increases, i.e.,
the amount of dye adsorbed onto a unit bed height (mass
transfer zone) increases with increasing ow rate leading to
Fig. 7 Breakthrough curves for adsorption of CR on CTAB/SD at
different pH values (C
0
= 50 mg L
-1
, v = 3 mL min
-1
, Z = 5.0 cm)
Fig. 8 Breakthrough curves for adsorption of CR on CTAB/SD at
different initial dye concentrations (pH = 6, v = 3 mL min
-1
and
Z = 5.0 cm)
Table 2 Values of breakthrough curve parameters obtained at dif-
ferent conditions
Operational parameters Adsorption parameters
V
b
(mL) q
b
(mg g
-1
) q
c
(mg g
-1
)
Initial concentration (mg L
-1
)
20 1,600 33.54 47.87
50 700 38.91 59.70
100 180 21.86 42.67
Flow rate (mL min
-1
)
3 700 38.91 59.70
6 450 22.92 42.71
12 300 19.96 33.60
Bed height (cm)
2.5 280 29.13 66.73
5 700 38.91 59.70
10.5 1,700 42.92 54.16
V
b
is the breakpoint volume, q
b
is the breakpoint adsorption capacity,
q
c
is the column adsorption capacity. Both q
b
and q
c
were calculated
using Eq. 3
J Surfact Deterg (2012) 15:557565 563
1 3
faster saturation at the higher ow rate [32]. Increasing the
bed height in the column was also led to a higher removal
efciency of CR dye. Higher uptake of dye at greater bed
heights can be due to an increase in adsorbent particles and
contact time of dye molecules with the adsorbent particles
which provides more binding sites and binding time for the
sorption.
Desorption Study
To make the adsorption process more economical, it is
necessary to regenerate the spent adsorbent. Moreover
desorption process of the dye can help the researcher in
elucidating the mechanism of an adsorption process. For
the desorption study, the dye uploaded columns were
treated with different chemicals. Maximum desorption was
observed when ethanol was employed as washing or re-
generant solution (% desorption [98). The fact that the
desorption process occurred using ethanol, an organic
agent, conrms that adsorption of CR onto CTAB/SD
mostly occurred via a chemisorption mechanism [32].
Conclusions
It was found that modication of sawdust by cationic
surfactant (CTAB) via simple treatment leads to a great
increase in sorption capacity of sawdust for uptake of
Congo Red dye from aqueous solutions. Electrostatic for-
ces between the positively charged active sites in CTAB
modied sawdust and the negatively charged adsorbate in
solution (CR) seems to be the main reason for the sorption
improvement. Maximum adsorption occurred at pH = 2.0
for SD and pH = 6.0 for CTAB/SD adsorbents. Adsorption
of CR on CTAB/SD followed the Freundlich model, while
adsorption of SD followed the Langmuir adsorption model.
The maximum adsorption capacities of SD and CTAB/SD
were found to be 5.2 and 9.1 mg g
-1
, respectively, based
on the monolayer Langmuir model which implies the
chemisorption mechanism. From adsorption experiments
performed in column or non-equilibrium conditions, it was
found CTAB/SD is much more efcient than SD when
compared in the batch system.
The results showed an increase in adsorption capacity
with an increase in initial dye concentration and bed height,
and sorption capacity decreased with increasing ow rate.
The highest bed capacity of 66.73 mg g
-1
was obtained
using 50 mg L
-1
inlet dye concentration, 2.50 cm bed
height and 3.0 mL min
-1
ow rate. Desorption studies
with the column system for CTAB/SD suggested that most
of the dye was held by CTAB/SD via strong electrostatic
forces, chemisorption as well as ion exchange processes.
CTAB/SD seems to be a cost effective, efcient, and very
promising adsorbent for the removal of anionic dyes from
dye polluted wastewaters such as textiles efuents.
Acknowledgments The authors would like to acknowledge nan-
cial support from the Postgraduate Studies of University of Guilan,
Rasht, Iran.
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Author Biographies
Reza Ansari (Ph.D.) is an associate professor in analytical chemistry.
His elds of interest: water and wastewater treatment, green
chemistry, electrochemistry and preparation electrochemical sensors
for environmental monitoring. Chemistry Department, University of
Guilan.
Babak Seyghali is a graduated M.Sc. student in the eld of
environmental analytical chemistry, Chemistry Department, Univer-
sity of Guilan.
Ali Mohammad-Khah (Ph.D.) is an assistant professor in analytical
chemistry. His elds of interest: environmental chemistry, pollution
control, and electrochemistry, University of Guilan.
M. Ali Zanjanchi (Ph.D.) is a full professor in analytical chemistry.
His elds of interest: spectroscopy, porous materials, and the
application of photocatalysis in pollution remediation. Chemistry
Department, University of Guilan.
J Surfact Deterg (2012) 15:557565 565
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