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2
1 1
(2)
This is the integrated rate law for a pseudo-second
order reaction. Equation (2) can be rearranged to
obtain
2
2
1
t
e e
t
q
t
q K q
=
+
...(3)
This has a linear form:
t
q q K q
t
e e t
+
=
1 1
2
2
...(4)
where h (mgg
-1
.min
-1
) can be regarded as initial
sorption rate as
q
t
/t 0, hence
h = K
2
q
e
2
(5)
Eq. (5) can be written as
t
q h q
t
e t
+ =
1 1
(6)
Eq. (6) may be transformed into the following four
forms
17
:
Type 1
1 1
t e e
t t
q Kq q
= +
...(7)
Type 2
2
1 1 1 1
t e
e
q t q
Kq
= +
(8)
Type 3
1
t
t e
e
q
q q
Kq t
=
(9)
Type 4
2
t e e t
q Kq Kq q =
(10)
Equations 7-10 were used to model the sorption
kinetics of Pb(II) and Cd(II) ions removal from
aqueous solutions using unmodified and chemically
modified oil palm fruit fibre adsorbents. The best
fitting equation for the experimental data for the
sorption of the two metals was determined using the
coefficient of determination, r
2
. For which
17
Eq. (11)
represents;
( )
( )
( )
2
2
2
2
m t
m m t t
q q
r
q q q q
=
+
...(11)
where q
m
is the amount of metal ion on the surface of
the oil palm adsorbent at any time, t (mg/g) obtained
from the pseudo-second order kinetic model, q
t
is the
amount of metal ion on the surface of the oil palm
fruit fibre adsorbent at time t, (mg/g) obtained from
the experimental data and q
is the average of q
t
(mg/g).
Results and Discussion
The surface characteristics of the unmodified and
chemically modified oil palm fruit fibre adsorbents
are presented in Table 1. The extent to which the oil
INDIAN J. CHEM. TECHNOL., JULY 2008
344
palm fruit fibre waste were chemically modified using
0.5 M and 1.0 M mercaptoacetic acid solutions was
estimated using the percentage thiol content (%SH).
This estimates the extent to which the mercaptoacetic
acid incorporated the thiol (SH) group onto the
surface of the chemically modified adsorbents. The
functional groups on the oil palm fruit fibre wastes are
phenolic, carboxylic and hydroxyl groups
21
. Thus, the
incorporation of the thiol functional group is to
increase the concentration of the metal binding sites
on the surface of the adsorbent. Studies have also
indicated that the incorporation of thiol groups on an
adsorbent matrix enhances the binding capacity of the
adsorbent by increasing the number of possible
binding sites for metal ion sorption
22
. From Table 1, it
can be seen that the percentage thiol content of the
chemically modified adsorbents increased with
concentration of the modifying reagent.
The specific surface area of the three oil palm fruit
fibre wastes is presented in Table 1. It can be seen
that the specific surface area of the adsorbents
increased with chemical modification. It has been
reported that acid modification of a biomass provides
the sorbent with larger surface area and enhanced
porosity which aids metal ion sorption
23
. Thus, the
increase in the specific surface area of the adsorbents
with chemical modification should enhance the
sorption capacity of the adsorbent. The pH point of
zero charge was also determined for the three
adsorbents and is also presented in Table 1. The pH
point of zero charge (pH
pzc
) of an adsorbent is the pH
of an adsorbent suspension at which the surface acidic
(or basic) functional groups of an adsorbent no longer
contributes to the pH of the suspension
24
. It may also
be said to be the pH at which the charge on the solid
surface of the adsorbent is zero. Above pH
pzc
the
surface charge of the adsorbent is negative
25
. There
exist a relationship between the value of the pH
pzc
of
an adsorbent and its adsorption capacity. The
adsorption of cations on any adsorbent is greatly
favourable at a pH above the adsorbent pH
pzc
24
. From
Table 1, it can be seen that the value of the pH
pzc
is
reduced from 7.1 for UOPF adsorbent to 6.4 for 0.5
MOPF and 6.0 for 1.0 MOPF adsorbents. This trend
may be due to the increased negative charge
contribution of the thiol group to the adsorbents
surface.
Kinetic modeling of pseudo-second order equations
Kinetic modeling of metal ion sorption for the
removal of an adsorbate from aqueous solution by an
adsorbent is often an attempt to determine the rate of
uptake and residence time of an adsorbate at the solid-
liquid interface. Therefore the sorption capacity and
required contact time are two of the most important
parameters that aid in the understanding of sorption
capability or by the character of sorbent in terms of
kinetics
26
.
The kinetic modeling for the sorption of Pb(II) and
Cd(II) ions from aqueous solution by the oil palm
fibre waste adsorbents was carried out using the
pseudo-second order equation. The type 1, type 2,
type 3 and type 4 equations of the pseudo-second
order were used
17
. The choice of the pseudo-second
order model for the analysis of the kinetics of Pb(II)
and Cd(II) ions is based on the fact that the pseudo-
second order equation has been applied to a
wide range of metal-sorbent systems with high
efficiency
30-32
. The type 1-4 pseudo-second order
linear models for the sorption of Pb(II) ion from
aqueous solutions by the three oil palm fruiting fibre
adsorbents are illustrated in Figs 1-4. An inspection of
the figures shows that the type 1 pseudo-second order
plot was the most linear of the kinetic models. From
the figures, the values of the pseudo-second order
kinetic model constant, K
2
, the amount of Pb(II) ion
adsorbed by each adsorbent at equilibrium, q
e
and the
initial sorption rate, h computed from the slope and
intercept values of Figs 1- 4 are presented in Table 2.
Examination of the values of the constants in
Table 2 using the kinetic model fitting parameter, the
coefficient of determination indicates that the value of
the type 1 pseudo-second order equation plot was the
highest. The selection criterion was that the closer the
r
2
value of a kinetic equation to unity, the greater the
fitting pattern of that model to the experimental
kinetic data. For the UOPF adsorbent the r
2
value of
the type 1 equation was highest. Same pattern was
also observed for the 0.5 MOPF and 1.0 MOPF
adsorbents. The pseudo-second order kinetic plot for
the four types of linear equations for the sorption of
Cd(II) ion from aqueous solution by the oil palm fruit
fibre is depicted in Figs 5-8. From these plots the
value of the slope and intercept were computed
Table 1 Surface characteristics of oil palm fruits
fibre waste adsorbents
Parameter UOPF 0.5 MOPF 1.0 MOPF
Specific surface area (m
2
g
-1
) 248.42 289.83 331.23
Thiol content (%SH) 1.35 2.83
pH
pzc
7.1 6.4 6
ABIA & ASUQUO: OIL PALM FRUIT FIBRE FOR SORPTION OF Pb(II) & Cd(II)
345
Fig. 1 Type 1-pseudo-second order linear model for Pb(II) ion
on oil palm adsorbents
Fig. 2 Type 2-pseudo-second order linear model for Pb(II) ion
sorption on oil palm adsorbents
Table 2 Pseudo second order kinetic parameters for Pb(II) on oil palm adsorbents
h (mg/g.min
-1
) r
2
Adsorbent Type q
e
(mg/g) K
2
(g/mg.min
-1
)
2.459 0.9998
UOPF 1 4.873 1.03x10
-1
3.663 0.9062
2 4.800 1.58x10
-1
3.690 0.8921
3 4.785 1.65x10
-1
3.318 0.8921
4 4.811 1.43x10
-1
0.5 MOPF 1 5.178 7.10x10
-2
1.906 0.9997
2 5.081 1.02x10
-1
2.644 0.9087
3 5.070 1.03x10
-1
2.655 0.9000
4 5.106 9.23x10
-2
2.407 0.9000
1.0 MOPF 1 5.197 6.45x10
-2
1.743 0.9989
2 5.037 1.20x10
-1
3.058 0.8628
3 5.028 1.20x10
-1
3.042 0.8297
4 5.579 6.81x10
-1
2.120 0.9045
Fig. 3 Type 3 -pseudo-second order linear model for Pb(II) ion
sorption on oil palm adsorbents
Fig. 4 Type 4 pseudo-second order linear model for sorption of
Pb(II) ion on oil palm adsorbents
INDIAN J. CHEM. TECHNOL., JULY 2008
346
and used to determine the pseudo-second order kinetic
model constant, K
2
, the amount of cadmium ion
sorbed at equilibrium, q
e
and the initial sorption rate,
h. The values of these constants are presented in
Table 3. Also, the analysis of these equations
indicated that for UOPF, 0.5 MOPF and 1.0 MOPF
adsorbents the type 1 pseudo-second order equation
was the best fit with coefficient of determination
value of unity for all three adsorbent systems.
Thus, the type 1 pseudo-second order equation is
the best kinetic model for the description of the
mechanism of Cd(II) on Pb(II) ions from aqueous
solutions. Previous work on the sorption of cadmium
by tree fern
17
has also shown that the type 1 pseudo-
second order equation was the best fit kinetic model.
In addition, it can be observed from Tables 2 and 3,
that the values of q
e
(mg/g) for each metal ion in
respect of the three adsorbents indicates a trend of
which can be given as 1.0 MOPF > 0.5 MOPF >
UOPF. Indicating that the values of q
e
for the
1.0 MOPF adsorbent for each metal ion is the highest.
This lends credence to the observation that chemical
modification of an adsorbent increases the adsorbent
capacity for the metal ion. Thus, the 1.0 MOPF
adsorbent had the highest efficiency because the
chemical modification process incorporated more
metal ion binding site onto the adsorbent matrix than
the 0.5 MOPF and the UOPF adsorbents of which the
later was not modified. Another inference that can be
drawn from data in Tables 2 and 3, is that
comparatively, the q
e
values for Cd(II) are higher than
that for Pb(II). This marked variation in the values of
the amount of each metal ion sorbed at equilibrium,
q
e
(mg/g) may be attributed to the differences in their
ionic sizes. The ionic radius of Pb(II) is 1.20 A and
that of Cd(II) is 0.97A.
It has been observed that when there is electrical
attraction between adsorbates and adsorbents, ions
Fig. 5 Type 1- Pseudo-second order model for Cd(II) sorption
on oil palm adsorbents
Fig. 6 Type 2- Pseudo-second order kinetic equation for Cd(II)
ion sorption on oil palm adsorbents
Fig. 7 Type 3- Pseudo-second order kinetic model for Cd(II)
ion sorption on oil palm adsorbents
Fig. 8 Type 4- Pseudo-second order kinetic model for Cd(II)
ion sorption on oil palm adsorbents
ABIA & ASUQUO: OIL PALM FRUIT FIBRE FOR SORPTION OF Pb(II) & Cd(II)
347
with small ionic radii but higher ionic charge are more
strongly attracted to sites of opposite charge
(adsorbent). However, for ions of similar charge, the
hydrated radius of the hydrated metal ions determines
the order of preference. For sorption, metal ions of
smaller ionic radii move more readily closer to
potential adsorption sites
32
. Thus, since Cd(II) ion has
a smaller ionic radius than Pb(II) it, therefore, has
greater ease to be sorbed onto the surface of the three
oil palm fruit fibre adsorbents. Hence, Cd(II) shows
higher q
e
value as compared to that of Pb(II), because
it has the greater affinity to the reactive sites of the
adsorbents. Similar, result was also observed in the
sorption of Cd(II) and Zn(II) ions on the biomass of
Manihot sculenta Crantz wastes
6
.
Conclusion
This study indicated that mercaptoacetic acid
modified and unmodified oil palm fruit fibre waste
could be used as adsorbents for the removal of Pb(II)
and Cd(II) ions from aqueous solutions. The kinetics
of sorption indicates that the pseudo second order
model can be used to describe the mechanism of
sorption of Pb(II) and Cd(II) ions. Modeling of the
type 1-4 equations of the pseudo-second order model
using the coefficient of determination, as the fitting
parameter indicates that the type 1 pseudo-second
order equation was the best fit for the description
of the mechanism of Cd(II) and Pb(II) ions
from the bulk solution to the adsorbent surfaces.
Chemical modification of the adsorbent also
increased the amount of the metal adsorbed at
equilibrium.
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Table 3 Pseudo second order kinetic parameters for Cd(II) on oil palm adsorbents
Adsorbent Type q
e
(mg/g) K
2
(g/mg.min
-1
) h (mg/g.min
-1
) r
2
UOPF 1 7.199 1.27x10
-1
6.618 1.0000
2 7.199 1.51x10
-1
7.836 0.9767
3 7.160 1.57x10
-1
8.070 0.9704
4 7.167 1.52x10
-1
7.838 0.9704
0.5 MOPF 1 7.564 1.62x10
-2
9.302 1.0000
2 7.674 1.34x10
-1
7.930 0.9430
3 7.553 1.77x10
-2
10.137 0.9535
4 7.563 1.62x10-2 9.679 0.9535
1.0 MOPF 1 7.855 2.08x10
-2
12.835 1.0000
2 7.980 1.68x10
-1
10.741 0.9578
3 7.846 2.17x10
-1
13.413 0.9912
4 7.848 2.15x10
-1
13.298 0.9912
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