You are on page 1of 14

ISSN: 1573-4377

ADSORPTION KINETICS AND MODELING OF CU(II) ION


SORPTION FROM AQUEOUS SOLUTION BY MERCAPTOACETIC
ACID MODIFIED CASSAVA (MANIHOT SCULENTA CRANZ)
WASTES

A.A. Augustine*, B.D. Orike and A.D Edidiong

Department of Pure and Industrial Chemistry, University of Port Harcourt, P. M. B. 5323,


Choba Port Harcourt, Nigeria.

ABSTRACT
The rate of removal of Cu(II) ions from aqueous solution by mercaptoacetic acid modified
cassava wastes (0.5MCF and 1.0MCF) was studied in batch conditions. The rate of sorption
of copper was rapid initially within 5-15 minutes and reached a maximum in 30 minutes.
Kinetic modeling analysis of the Elovich, pseudo-first order, pseudo-second order,
intraparticle diffusion, mass transfer and intraparticle diffusivity equations using the linear
coefficient of determination r2 values showed that the pseudo-second order equation was the
most appropriate model for the description of Cu(II) transport. Thus the sorption of Cu(II)
ion can be said to follow a pseudo-second order model, with chemical sorption as its rate
limiting step. The initial adsorption rate values were: 2.94 x 10-1 and 2.60 x 10-1 mg.g-
1.min-1 for 0.5MCF and 1.0MCF adsorbents respectively.

KEYWORDS:
Copper, kinetic modeling, sorption, cassava waste, mercaptoacetic acid.

INTRODUCTION
The increased level of environmental contamination as a consequence of industrial
development is posing a very serious problem to the global environment. Industrial process
for extracting metals or, more generally, all processes involving metals in their productive
cycle generate significant heavy metal cations [1]. Mine drainage, metal industries, refining,
electroplating, dye and leather industries, domestic effluents, land fill leachate, and
agricultural run off all generate wastewater that contain heavy metal ions [2]

The presence of these heavy metals in the environment has led to a number of environmental
problems. Since most of these heavy metal are non-degradable into nontoxic end products,
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

their concentrations in effluents must therefore be reduced to acceptable levels before


discharging them into the environment. Otherwise these metal ions could pose threats to
public health and or affect the aesthetic quality of potable water. According to World Health
Organisation (WHO), the metals of most immediate concern are chromium, copper, zinc,
iron, cadmium and lead [3].

Since copper is a widely used material, there are many actual or potential sources of copper
pollution. Copper is used in Jewelry, paints, pharmaceutical products, wood preservatives,
pigments, metal works, petroleum refinery, motor vehicle and aircraft plating and finishing.
Also copper may be found as a contaminant in food, especially shellfish, liver, mushroom,
nuts and chocolate. In addition, any processing method or container using copper material
may contaminate the product, such as food, water or drink [4].

Copper is essential to human life and is required for various biological processes, but like all
heavy metals, is potentially toxic as well [5].

In order to solve the problems of heavy metal pollution in the ecosystem, it is important to
bring pragmatic solutions to the issue. There are several methods for treatment of metal
contaminated effluents such as precipitation, ion exchange, membrane processes and
adsorption. Since the selection of wastewater treatment methods is based on the
concentration of waste and the cost of treatment, adsorption is often the method of choice for
removal of heavy metals from wastewater [6].

Furthermore, to enhance the cost effectiveness of the adsorption process for heavy metal
treatment, various agricultural by-products have been developed as low-cost sorbents.
These include: groundnut husk [7], shea butter seed husk [8], wild cocoyam [9], palm
kernel fibre [10] and fluted pumpkin [II]

In this study, an agricultural by-product, cassava waste in its chemically modified form
which is obtained from the processing of cassava tuber (Manihot sculenta cranz) a staple
food in Nigeria will be used to remove Cu(II) ions from aqueous solution. Interest in this
work will be on the kinetics of Cu(II) ion removal. This is because sorption kinetics is an
important parameter in wastewater treatment. Since sorption kinetics can be used to predict
the rate of pollutant removal from aqueous solutions in the design of appropriate sorption
treatment plants [12]. The different kinetic models that will be used to analyse the kinetic
data for Cu(II) ion sorption are, pseudo-first order [13], the pseudo-second order [14],
Elovich [15-16], mass transfer [17], intra-particle diffusion [18-19] and intra-particle
diffusivity [20].

MATERIALS AND METHODS


Adsorbent
Cassava fibre waste obtained from the processing of cassava into the staple food “garri” was
obtained from a cassava processing mill in a village near Port Harcourt, Rivers State,
Nigeria. The cassava fibre waste was airdried and ground using a wiley mill grinder. The
powdered cassava fibre was washed with deionized water and wet sieved through a set of
sieves (106 and 105µm) and airdried.

2222
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

Dissolutions
All reagents used for sorption studies were of analytical reagent grade. 1000mg/L of
Copper(II) ion stock solution [CuS04.5H20] (BDH) was prepared by diluting a known mass
in doubly distilled-deionized water in a 1000cm3 volumetric flask and made up to mark.
From the stock solution 30mgL-1 working solutions of Cu(II) ions were prepared by serial
dilution.

Adsorbent Activation and Chemical Modification


The sieved cassava fibre waste was soaked in excess 0.3M trioxonitrate (v) acid (HNO3)
solution for 24 hours. It was later filtered airdried and sieved through the mesh sieves. The
powdered cassava fibre waste was then divided into two portions (1 and 2) each weighing
20g. The first portion “1” was soaked in excess 0.5M mercaptoacetic acid solution, while
portion “2” was also soaked in excess solution of 1.0M mercaptoacetic acid according to the
procedure described in [13]. The two mixtures were later filtered after 24 hours, air dried
and labeled as 0.5MCF and 1.0MCF for the 0.5M and 1.0M mercaptoacetic acid modified
cassava fibre waste respectively.

Experimental Procedure
Kinetic sorption studies were carried out using 100ml of Cu(II) ion solutions of initial
concentration 30mg/dm3. The metal ion solutions were measured into different labeled
conical flasks containing 1.0g of each adsorbent (0.5MCF and 1.0MCF). The different
flasks were corked and uniformly agitated in a EFL-MK3 shaker at a speed of 25 rpm at a
temperature of 280C and pH of 5.0 for 5 minutes. The experimental set up was thereafter
repeated for various other time intervals of 10, 15, 20, 25 and 30 minutes. Also kinetic
infinity sorption (α) was also carried out for 24 hours. At the end of each contact time, the
content of each flask was filtered using a whatman No. 41 filter paper. The concentration of
(Cu(II) ion in each filtrate was determined using a Buck scientific flame atomic absorption
spectrophotometer (FAAS) model 200A.

Data analysis
The metal sorption capacity (qt) of the mercaptoacetic modified cassava fibre wastes was
calculated from the relationship [22] in eqn (1):

qt =
(c i " c t )
Ms (1)

Also, the percentage of Cu(II) ions removed (%RE) from the aqueous solution by each of
! the two adsorbents (0.5MCF and 1.0MCF) was calculated using eqn (2):

%RE =
(c i " c t ) #100
ci (2)

! Whereas the fraction of Cu(II) ions removed by the two adsorbents was determined from the
relationship [23].

2223
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

YT =
(c i " c t ) (3)
(c i " c e )
where qt is the metal sorption capacity of the adsorbent (mg/g), Ci is the initial metal ion
concentration (mg/L), Ct is the metal ion concentration in solution at time t (mg/L), Yt is the
! fraction of the metal adsorbed at time t, Ms is the weight of the adsorbent (g), V is the
volume of the metal ion solution used for sorption (dm3) and Ce is the concentration of metal
ion, when sorption is completed, ie infinity sorption [ C∞ = Ce]

Kinetic Modeling
The study of sorption kinetics describes the adsorbate uptake rate and evidently this rate
controls the residence time of adsorbate at the solid liquid interface [3]).

The kinetics of Cu(II) ion sorption on the two mercaptoacetic acid modified cassava
adsorbents was analysed using different kinetic models, these include: the pseudo-first order
[13], pseudo-second order [14], Elovich [15-16], mass transfer [17], intraparticle diffusion
[18-19], and intraparticle diffusivity [20].

The Pseudo-First Order Equation


The pseudo-first order equation [13], is generally expressed as:

dqt
= k1 (qe " qt ) (4)
dt

Where qe and qt are the sorption capacities at equilibrium and at time t, respectively (mgg-1)
and K1 is the rate constant of pseudo-first order sorption (Lmin-1). After integration and
! applying boundary conditions t = 0 to t = t and qt = 0 to qt = qt, the integrated form of
equation (4) becomes:

log(qe " qt ) = logqe " k1t (5)

When the values of log (qe – qt) were linearly correlated with t, the plot of log (qe - qt) versus
! t will give a linear relationship from which k and q can be determined from the slope and
1 e
intercept of the graph respectively.

The Pseudo- Second Order Equation


The pseudo-second order chemisorption kinetic equation [14] is expressed as eqn 6:

dqt 2
= k2 (qe " qt ) (6)
dt

!
2224
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

Where qe and qt are the sorption capacity at equilibrium and at time t, (mgg-1) respectively
and K2 is the rate constant of the pseudo-second order sorption (g.mg-1. min-1). For the
boundary conditions t = 0 to t = t and qt = 0 to qt = qt, the integrated form of eqn (6)
becomes:

1 1
= + k2 t (7)
qe " qt qe

Which is the integrated rate law for a pseudo-second order reaction. Eqn (7) can be
! rearranged to obtained:

1
qt = (8)
1 t
2
+
k2qe qe

Which has a linear form:


! 1 1 t
= 2
+ (9)
qt k2qe qe

-1 -1
! Where h (mg.g . min ) can be regarded as the initial sorption rate as qt/t→0 hence

h= K2qe2 (10)

Furthermore eqn(9) can be written as:


t 1 t
= + (11)
qt h qe

If the pseudo-second order kinetics is applicable to the experimental data, the plot of t/qt
versus t of eqn (II) should give a linear relationship from which qe, k and h can be
! determined from the slope and intercept of the plot respectively.

The Elovich Kinetic Equation


The Elovich equation [15-16] is generally expressed as:

dqt
= "e# $q t (12)
dt

Where qt is the sorption capacity at time t (mgg-1), α is the initial adsorption rate (mg.g-1.
min-1) and, β is the desorption constant (mg.g-1.min-1) during any one experiment.
!
To simplify the Elovich equation [15] assumed α β t > > 1 and by applying boundary
conditions qt = 0 at t = 0 and qt = qt and t = t, [16] eqn (14) becomes:

2225
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

1 ln("# ) ln t
= + q (13)
qt # #

Thus, if a plot of qt versus ln t is linearly correlated, the constants α and β can be computed
! from the slope and intercept of the graph.

Mass Transfer Equation


The mass transfer equation [17] is generally expressed as:

c o " c t = De K o t (14)

Where Co is the initial metal ion concentration (mg.dm-3), Ct is the metal ion concentration
at time t, t is the shaking time (mins), D is a fitting parameter, Ko is the adsorption constant
! which is related to the mass transfer adsorption coefficient, Ko = KM, where M is the mass
of the adsorbent (g).

A linearised form of eqn (14) is:

ln(c o " c t ) = ln D + K o t (15)

If the sorption of Cu(II) ions on the two adsorbent is depicted by the mass transfer model,
then a plot of ln (Co – Ct) versus time should give a linear relationship from where the
! constants lnD and K can be determined from the slope and intercept of the plot respectively.
o

The Intraparticle Diffusision Model


The intra-article diffusion [18-19] model is expressed as eqn: 16:

R = K id t a (16)

Where R is the percent Cu(II) ions adsorbed, t is the contact time, a is the adsorption
! mechanism, kid is the intra-particle diffusion rate constant (min-1). Kid may be taken as a rate
factor that is percent Cu2+ adsorbed per unit time [22]

A linear form of eqn 16 is:

log R = logK id + alog t (17)

The plot of log R versus log t (eqn 17) should give a linear relationship from where the
constants “a” and “Kid” can be determined from the slope and intercept of the plot,
! respectively.

2226
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

The Intra-particle Diffusivity Equation


The intra-particle diffusivity equation [20] for the description of sorption kinetics is

qt = X i + K 1t (18)

Where: K1 is the initial rate of sorption controlled by intra-particle diffusivity (mg.g-1. min-
1
). Xi depicts the boundary layer thickness. If the sorption of Cu(II) ions follows the intra-
! particle diffusivity equation, then a plot of q versus T1/2 should give a linear relationship
t
from where K1 and Xi can be determined from the intercept and slope of the plot
respectively.

RESULT AND DISCUSSION

Effect of Contact Time


Kinetics of metal ion sorption governs the rate, which determines the residence time and it is
one of the important characteristics defining the efficiency of an adsorbent [25]. The rate at
which sorption takes place is of most importance, especially when designing batch sorption
systems. Consequently it is important to establish the time dependency of such systems for
various pollutant removal processes [26]. Therefore, the required contact time for sorption
to be completed is important to give insight into a sorption process. This also provides
information on the minimum time required for considerable adsorption to take place and the
possible diffusion control mechanism between the metal ion as it moves from the bulk
solution towards the adsorbent surface.

The kinetic behaviour of Cu(II) ion sorption onto the two mercaptoacetic acid modified
cassava waste was examined using agitation times of 5 – 30 minutes. The removal
efficiency of the two adsorbents (0.5MCF and 1.0MCF) for Cu(II) ion is illustrated in
Figure 1, while the variation of sorption capacity (qt) of Cu2+ with contact time for the
adsorbents is shown in Figure 2. It can be seen from the figures that the removal efficiencies
of the adsorbents for Cu(II) ion after 25 minutes were 20.33% and 21.00% for 0.5MCF and
1.0MCF adsorbents respectively.

Thus, the rate of Cu2+ removal was quite rapid initially, but it gradually becomes slower
with passage of time reaching a maximum in 30 minutes. The initial faster rate may be due
to the availability of the uncovered surface area of the adsorbent initially, since adsorption
kinetics depends on the surface area of the adsorbent [27]. In addition, the variation in the
amount of Cu(II) ion removed by the two adsorbents could be related to the nature and
concentration of the surface groups (active sites) responsible for interaction with the copper
ions.

2227
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

O.5MCF 1.0MCF 0.5MCF 1.0MCF

25 0.70

24
0.65
23

Sorption capacity(mg/g)
22 0.60

21
%Removal

0.55
20

19
0.50
18

17 0.45

16
0.40
15 0 5 10 15 20 25 30 35
0 5 10 15 20 25 30 35 Time(mins)
Time(mins)
Fig.2: Cu2+ Sorption capacity(qt) variation w ith contact time for
Fig. 1: Percentage removal of Cu2+ with time for different adsorbents adsorbents

The cassava waste adsorbent contains abundant cellulosic units including a matrix of: OH-,
COO-, CN- and NH2 functional groups that take part in metal ion binding [28]. Also, during
chemical modification process the thiol (SH) was incorporated onto the cassava waste using
mercaptoacetic acid, thereby increasing the concentration of surface active sites on the
adsorbent matrix.

0.5MCF 1.0MCF

0.7

0.65

0.6

0.55
Yt

0.5

0.45

0.4
2 2.5 3 3.5 4 4.5 5 5.5 6

T1/2.min1/2
Fig.3: Time -dependence of the fraction of adsorption of Cu2+ for various
adsorbents

Figure 3 depicts the time-dependence of the fraction of adsorption of Cu(II) ions on the two
adsorbents. It can been seen from the figure that as T1/2 increases, the rate fraction of
adsorption (Yt) also increases. This indicates that with passage of time, a higher fraction of
the Cu(II) ions migrates from the bulk solution through the adsorbent boundary layer onto
the active sites of the adsorbent and is adsorbed. This enhanced sorption of the metal ion
with increase in agitation time may be due to the decrease in boundary layer resistance to
mass transfer in the bulk solution and an increase in kinetic energy of the hydrated metal ion
[29].

2228
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

Kinetic Modeling of Cu2+ Sorption


Many attempts have been made to formulate a general expression describing the kinetics of
sorption on solid surfaces for liquid-solid phase sorption on solid systems. This has led to
the existence of a series of kinetic equations that are used to model metal ion transport onto
adsorbent surfaces

Modeling of kinetic data is fundamental for the industrial application of sorption since it
gives information for comparison among different biomaterials under different operational
conditions for designing and optimizing operational conditions for pollutant removal from
wastewater systems. [30].

In order to investigate the mechanism of sorption of copper by the modified cassava wastes
and the potential rate-controlling steps, such as mass transport and chemical reactions,
kinetic models were used to model the transport of copper. The different kinetic models
used were, pseudo-first order, pseudo second order, Elovich, intra-particle diffusion, mass
transfer, and intra-particle diffusivity.

0.5MCF 1.0MCF
0.5MCF 1.0MCF
50
Time(mins)
0.00
0 5 10 15 20 25 30 35
-0.05 40

-0.10

-0.15 30
t/qt

-0.20
log(qe-qt)

-0.25 20

-0.30

-0.35 10

-0.40

-0.45 0

-0.50 0 5 10 15 20 25 30 35
Time(mins)
2+
Fig.4: Pseudo-first order kinetics of Cu2+ on different adsorbents Fig.5:Pseudo-second order kinetics of Cu on different adsorbents

The pseudo-first order plot of Cu2+ on the cassava waste adsorbents is illustrated in Figure
4. From the plot the pseudo-first order rate constant, K1 and the sorption capacity, qe were
computed from the slope and intercept of the plot and presented in Table 1. It can be seen
that the values of the pseudo-first order rate constant increased with chemical modification.
While the sorption capacity, qe values decreased with chemical modification. Figure 5
depicts the plot of t/qt versus contact time for the pseudo-second order equation for sorption
of Cu(II) ions. From the plot the values of the pseudo-second rate constant K2, the initial
adsorption rate h and the sorption capacity qe computed from the slope and intercept are
presented in Table 2. It can be seen that the values of K2 and h decreased with chemical
modification, while the sorption capacity qe, increased with chemical modification.

2229
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

Table 1: Kinetic constants for pseudo-first order Equation.


Adsorbent k1 (L.min-1) qe (mg.g-1)
0.5MCF 1.15 X 10-2 1.973

1.0MCF 1.17 X 10-2 1.676

Table 2: Kinetic parameters for pseudo-second order Equation.


Adsorbent qe (mg.g-1) k2 (g.mg-1. min-1) h (mg.g-1. min-1)
0.5MCF 0.669 6.56 X 10-1 2.94 X 10-1

1.0MCF 0.703 5.25 X 10-1 2.60 X 10-1

Table 3: Kinetic constants for Elovich Equation


Adsorbent α (mg.g-1. min-1) β (mg.g-1.min-1)
0.5MCF 6.48 X 10-2 15.822

1.0MCF 7.40 X 10-2 13.900

The Elovich equation plot for Cu(II) ion sorption is shown in Figure 6. Table 3 shows the
constants of the Elovich equation α the initial adsorption rate and β the desorption capacity
that were obtained from the slope and intercept of the Elovich plot. It can be seen that the
initial adsorption rate increased with chemical modification. While the desorption constant
decreased with chemical modification. Since adsorption and desorption are interrelated in
surface transport, it can be said that there exist an inverse relationship between α and β as
presented in Table 3.

0.5MCF 1.0MCF
0.5MCF 1.0MCF
0.68
1.36
0.66
1.34
0.64
1.32
0.62
1.3
qt(mg/g)

0.60
Log R

1.28
0.58
1.26
0.56

0.54 1.24

0.52 1.22

0.50 1.2
2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60 0.6 0.8 1 1.2 1.4 1.6
ln time Log T

Fig.6: Elovich sorption model for Cu2+ on different adsorbents Fig. 7:Intraparticle Diffusion kinetics for Cu2+ sorption onto different
adsorbents

Figure 7 shows the plot of Log R (percent removal) versus Log T for the description of the
intra-particle diffusion kinetics of Cu(II) removal. The computed values of the constants,
the intra-particle diffusion constant (Kid) and the adsorption mechanism (a) are presented in
Table 4. The values show that both constants increased with chemical modification. The
mass transfer plot of ln (Co-Ct) versus time is seen in Figure 8. The fitting parameter (ln D)
that is a measure of the apparent distribution ratio, the adsorption constant Ko and the mass

2230
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

transfer adsorption coefficient Km values were computed from the slope and intercept and
are presented in Table 5. From the table it can be seen that the values of lnD, Ko and Km
increased with chemical modification. The increase in the value of lnD, which is a measure
of the apparent distribution ratio of the Cu(II) ion between the bulk solution and the
adsorbent surface portrays that as chemical modification of the adsorbent increases a higher
concentration of the Cu(II) ions are transported from the bulk solution onto the active sites
of the adsorbent particles.

Table 4: Kinetic parameters for Intra-particle Diffusion Equation


Adsorbent Kid (min-1) A
0.5MCF 14.01 1.09 X 10-1

1.0MCF 14.41 1.10 X 10-1

Table 5: Kinetic constants for mass transfer Equation


Adsorption lnD Ko (min-1) km (g.L-1.min-1)
0.5MCF 1.604 7.0 X 10-3 3.50 X 10-3

1.0MCF 1.610 9.1 X 10-3 4.55 X 10-3

The intra-particle diffusivity equation for the description of the sorption of Cu(II) ions from
the aqueous solution onto the surface of the cassava waste adsorbents (0.5MCF and
1.0MCF) is shown in Figure 9. From the slope and intercept of the plot, the values of the
initial sorption rate K1 and the boundary layer thickness, Xi were computed and presented in
Table 6. Examination of Table 6 shows that the values of the initial sorption rate increased
with chemical modification, while that of the boundary layer thickness decreased with
chemical modification. Thus it can be said that there is a decrease in boundary layer
thickness (Xi) between the bulk solution and the adsorbent particle as the initial adsorption
rate (K1) of Cu(II) ion increases. Hence there is said to exist an inverse relationship
between, the initial sorption rate k1 and the boundary layer thickness, Xi which leads to the
observed pattern of Cu(II) ion sorption from the intra-particle diffusivity equation.

Table 6: Kinetic parameters for Intra-particle Diffusivity Equation


Adsorbent K1(mg.g-1.min-0.5) X1
0.5MCF 3.62 X 10-2 4.29 X 10-1

1.0MCF 4.15 X 10-2 4.22 X 10-1

2231
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

0.5MCF 1.0MCF
0.5MCF 1.0MCF 0.68

2.00 0.66
1.95
0.64
1.90
0.62
1.85

q t (mg/g)
1.80 0.6
ln(Co-Ct)

1.75
0.58
1.70
0.56
1.65

1.60 0.54

1.55 0.52
1.50
0 5 10 15 20 25 30 35 0.5
2 2.5 3 3.5 4 4.5 5 5.5 6
Time(mins)
T1/2.min1/2
Fig.8: Mass transfer kinetic model for Cu2+ on various adsorbents
Fig. 9:Intra-particle Diffusivity model for Cu2+ sorption on various adsorbents

Coefficient of Determination Analysis


For an appropriate description of the mechanism of Cu(II) ion sorption, it was necessary that
different kinetic models be tested to determine their extent of fitness to the experimental
sorption data. The optimization procedure to be able to select the best fit model requires the
selection of an error function in order to evaluate the fit of the kinetic models to the
experimental sorption data. The choice of error function can affect the parameters derived-
error functions based primarily on absolute deviation bias of the fit towards high
concentration data and this weighing increases when the square of the deviation is used to
penalize extreme errors. The coefficient of determination, r2 was chosen as the error
function for the kinetic model analysis. This is because linear regression implicitly
minimizes the sum of the squares of the errors to determine the equation parameters [31].

Table 7 presents the values of the linear coefficient of determination (r2) values of the
different kinetic models used to evaluate the sorption of Cu(II) onto the two modified
cassava waste adsorbents. Examination of Table 7 shows that the pseudo-second order
kinetic equation had the highest r2 values. Thus this kinetic model was taken as the best fit
equation for the description of the mechanism of sorption of Cu(II) ions. In addition,
examination of the sorption capacity values (qe) of the pseudo second order model shows
that the values were in the same range as the experimental sorption capacity values.

Therefore, the sorption of Cu(II) ions from aqueous solution onto the mercaptocacetic acid
modified cassava waste adsorbents was found to follow the pseudo-second order kinetic
equation. Similar conclusion was also reported for the sorption of some heavy metal ions
onto various adsorbent surfaces [32-35].

Furthermore, the pseudo-second order is based on the assumption that sorption follows a
second order mechanism, with chemsorption as the rate limiting step. So the rate of
occupation of adsorption sites is proportional to the square of the number of unoccupied
sites [4].

2232
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

Table 7:Linear coefficient of determination (r2) of kinetic models


Kinetic Model Adsorbent

0.5MCF 1.0MCF

Pseudo-first order 0.9804 0.9514

Pseudo-second order 0.9940 0.9896

Elovich 0.8848 0.8370

Intraparticle diffusion 0.9333 0.8087

Mass transfer 0.8867 0.9726

Intraparticle diffusivity 0.9512 0.9152

CONCLUSION
It appears that majority of sorption kinetic studies reported in literature often use one or two
models to test their data and then conclude on the appropriate model for their work.
However, it is the view in this study that metal ion sorption may be described by more than
one kinetic model. Thus it is necessary that several kinetic equations be used to model metal
ion sorption. A detailed analysis of six kinetic equations were used to investigate the
sorption of Cu(II) ions onto the chemically modified cassava wastes. From the kinetic
model analysis using coefficient of determination, the pseudo-second order model was the
most fitting for the description of Cu(II) ion transport from the bulk solution onto the surface
of the chemically modified cassava waste adsorbents.

REFERENCES

1. A. Fraile, S. Penche, F. Gonzalez, M. L. Blazquez, J. A. Munoz, A. Ballester. Biosorption of copper,


zinc, cadmium and nickel by Chlorella vulgaris. Chem. Ecol. 21, 61 (2005).
2. Z. Aksu, T. Kutsal, A comparative study for biosorption characteristics of heavy metals ions with (C.
vulgaris. Environ. Technol. 11,979 (1990)
3. WHO: World Health Organisation, report, Guidelines for drinking water quality, Geneva, 1984.
4. W. M. Antunes , A. S. Luna, C. A. Henriques, A. C. A. da Costa, An evaluation of copper biosorption
by a brown seaweed under optimized conditions. Electr. J. Biotech. 6, 174 (2003).
5. Y. Nuhoglu, E. Malkoc, A. Gurses, N. Canpolat. The removal of Cu(II) from aqueous solution by
Ulothrix zonata. Bioresour. Tech. 85, 331 (2002).
6. O. Yavuz, Y. Altunkaynak, F. Guzel. Removal of copper, nickel, cobalt and manganese from aqueous
solution by kaolinite. Water Res. 37, 948 (2003)
7. F. E. Okieimen, E. U. Okundia, D. E. Ogbeifun. Sorption of cadmium and lead ions on modified
groundnut (Arachis hypogea) husks. J. Chem. Tech. Biotechnol. 51, 97 (1991)
8. I. C. Eromosele, O. O. Otitolaye. Binding of Iron, Zinc, lead ions from aqueous solution by Shea
butter (Butyrospermum parkii) seed husks. Bull. Environ. Contam. Toxicol. 52, 530 (1994).
9. M. Horsfall Jr., A. I. Spiff. Effects of temperature on the sorption of Pb2+ and Cd2+ from aqueous
solution by Caladium bicolor (Wild cocoyam) biomass. Elect. J. Biotech. 8, 163 (2005).
10. E. A. Ofomaja, I. E. Unuabonah, N. A. Oladoja. Removal of lead from aqueous solution by palm
kernel fibre S. Afr. J. Chem. 58, 127 (2005).
11. M. Horsfall Jr., A. I. Spiff Adsorption of transition metals in aqueous solution by fluted pumpkin
(Telfairia occidentalis hookf) waste Chem Biodive. 2, 1266 (2005).

2233
Augustine et al. EJEAFChe, 6 (4), 2007. [2221-2234]

12. M. Horsfall Jr., A. I. Spiff. Kinetic studies on the sorption of lead and cadmium ions from aqueous
solutions by Caladium bicolor (Wild cocoyam) biomass. Bull. Chem. Soc. Ethiop. 19, 89 (2005).
13. S. Lagergren. About the theory of so-called adsorption of solution substances. kunglia srenska vertens
Ka psakademiens. Handlinger 24, 147 (1898).
14. Y. S. Ho, G. Mckay. A. two stage batch sorption optimized design for dye removal to minimize
contact time. Trans. IChem. E. 76, 313 (1998).
15. S. H. Chien, W. R. Clayton. Application of Elovich equation to the kinetics of phosphate release and
sorption on soils. Soil Sci. Amer. J. 44, 265 (1980)
16. D. L. Sparks. Kinetics of reaction in Pure and mixed systems. In: Soil Physical Chemistry Sparks, D.
L. (ed) CRC press, Boca Raton. Florida.
17. R. Qadeer, S. Akhtar. Kinetics study of lead ion adsorption on active carbon. Turk J. Chem. 29,
95(2005)
18. W. J. Weber, J. C. Morris. Kinetics of adsorption on carbon from solution. J. Sanit Eng. Div. Amer.
Soc. Eng. 89, 31 (1963)
19. S. K. Srivastava, R. Tuagi, N. Pant. Adsorption of heavy metal ions on carbonaceous materials
developed from water-slurry generated in Local fertilizer plant. Water Res. 13, 1161 (1989)
20. G. Mckay, V. J. Poots. Kinetics and diffusion processes in colour removal from effluent using wood
as an adsorbent. J. Chem. Technol. Biotechnol. 30, 279 (1980)
21. Okieimen, F. E., Maya, A. O., Oriakhi, C. O. Sorption of cadmium, lead and zinc ions on sulphur
containing chemically modified cellulosic materials. Inter. Environ. Anal. Chem. 32, 23 (1988).
22. E. Demirbas, M. Kobya, E. Senturk, T. Ozkan. Adsorption Kinetics for the removal of Chromium (vi)
from aqueous solutions on the activated carbons prepared from agricultural wastes. Water SA. 30, 533
(2004)
23. G. Karthikeyan, K. Anbalagan, A. N. Muthulakshmi. Adsorption dynamics and equilibrium studies of
Zn(II) onto Chitosan. J. Chem. Sci. 116, 119 (2204)
24. Y. S. Ho. Second order Kinetic model for the sorption of cadmium onto tree fern: A comparison of
linear and non-linear methods. Water Res. 40, 199 (2006)
25. K. A. Krishnan, Anirudhan, T. S. Removal of cadmium (II) from aqueous solutions by team-activated
sulphurised carbon prepared from sugar cane bagasse pith: Kinetics and equilibrium studies. Water SA
29(2), 147 (2003)
26. Y. S. Ho, C. T. Huang, H. W. Huang Agricultural by-product as a metal sorbent: sorption of copper
ions from aqueous solution onto tree fern. Biochem. 37(5), 1421 (2002).
27. J. M. Smith. Chemical Engineering Kinetics, Mc-Graw Hill, New York (1970).
28. M. Horsfall Jr, F. Ogban, E. E. Akpor honour, Sorption of Chromium (vi) from aqueous solution by
cassava. Chem. Biodiver. 3, 161 (2006)
29. M. Horsfall Jr., A. A. Abia. Sorption of Cadmium(II) and Zinc (II) ions from aqueous solution by
cassava waste biomass (manihot sculenta cranz). Water Res. 37, 4913 (2003)
30. B. Benguella, H. Ben asissa. Cadmium removal from aqueous solutions by Chitin: Kinetics and
equilibrium studies. Water Res. 36, 2463 (2002)
31. Y. S. Ho, J. F. Porter, G. Mckay. Equilibrium isotherm studies for the sorption of divalent metals ions
onto peat: copper, Nickel and lead single component systems. Water, Air and Soil Pollut. 141, 1
(2002)
32. B. Cordero, P. Lodeiro, R. Herrero, M. E. Sastrde Vi cente. Biosorption of cadmium by Fucus
spiralis. Environ. Chem. 1, 180 (2004)
33. M. Prasad, S. Sexena, Sorption mechanism of some divalent metal ions onto low-cost mineral
adsorbent Indus. Eng. Chem. Res. 43(6), 1512 (2004).
34. S. Y. Quek, D. A. J. Wase, C. F. Forster. The use of Sago waste for the sorption of lead and copper.
Water SA 24 (3), 251 (1998).
35. N. K. Lazaridis, D. D. Asouhidou. Kinetics of sorptive removal of chromium (vi) from aqueous
solutions by calcined Mg-Al-Coz hydrotalcite. Water SA 37(12), 2875 (2003)

2234

You might also like