International Journal of Technical Research and Applications e-ISSN: 2320-8163,

www.ijtra.com Volume 2, Issue 4 (July-Aug 2014), PP. 96-103

96 | P a g e
EQUILIBRIUM, KINETIC AND
THERMODYNAMIC STUDIES ON BASIC DYE
ADSORPTION USING COMPOSITE ACTIVATED
CARBON
Ejikeme, P.C.N., Ejikeme, Ebere M., Okonkwo, Gloria N.
Chemical Engineering Department,
Enugu State University of Science and Technology Enugu,
Enugu State Nigeria.
Abstract Batch adsorption experiments were carried out for
the adsorption of cationic dye from aqueous solution onto
composite activated carbon. The composite activated carbon was
prepared from brewers spent grain and sea bean shell at a ratio
of 1:1. The equilibrium studies were done at different
concentrations and temperatures. The equilibrium data were
fitted to Langmuir, Freundlich, Dubinin-Radushkevich, and
Temkin isotherm models. The results showed that both Lagmuir
and Freundlich isotherm model fitted the data reasonably well
but Freundlich isotherm fitted better in the temperature range
studied. This confirmed that the adsorption is heterogeneous,
non-specific and non-uniform in nature. Kinetic studies were also
undertaken in terms of first order, second order, pseudo first
order, pseudo second order, Elovich, Boyd, and intra-particle
diffusion models. The results indicated that the data followed
pseudo second order model with surface adsorption and intra-
particle diffusion concurrently operating during the adsorbate-
adsorbent interaction. The values of the thermodynamic
parameters computed from Vant Hoff plot confirmed the
process to be endothermic and spontaneous in nature.
Key words Activated carbon, basic dye, brewers spent grain,
sea bean shell.
I. INTRODUCTION
Several Industries generate wastewaters such as textile,
chemical, refineries, plastics, and food processing plants. These
wastewaters include residual dyes which are not bio-
degradable. It is estimated that more than 100,000
commercially available dyes with over 7 x 105 tonnes of dye
stuff produced annually [1], [2], [3]. These residual dyes, when
discharged into the environment, will become a serious threat.
Generally, many dyes can be used in textile industry, like basic
dyes, acid dyes, direct dyes, azo dyes, mordent dyes, vat dyes,
disperse dyes, and sulphur dyes [4], [5]. Methylene blue (MB)
is a basic dye heavily used in the textile industry [5].
Some specific effluents from industrial production
processes may be difficult to purify by traditional wastewater
treatment technology, as a result of the complexity of some of
their components [6]. Many methods are used to remove dyes
from wastewaters such as coagulation, membrane separation
process, electrochemical, chemical oxidation, reverse osmosis,
aerobic and anaerobic microbial degradation. These methods
have restrictions, and therefore, are not successful for removing
the color completely from wastewater [5], [7]. Among all these
methods, adsorption is preferred due to its low cost and high
treatment efficiency [8]
Activated carbon is the main adsorbent used in adsorption
processes. The adsorption capacity of the activated carbon and
also the performance of the activated carbon adsorption system
are usually predicted from equilibrium sorption isotherm [9].
An adsorption isotherm is an invaluable curve describing the
phenomenon governing the retention (or release) or mobility of
a substance from the aqueous porous media or aquatic
environments to a solid phase at a constant temperature and pH
[10], [11], [12]. Experimental data were fitted into different
isotherm models like; Langmuir, Freundlich, Dubinin-
Raushkevich and Temkin isotherm models.
The study of sorption kinetics in wastewater treatment is
significant as it provides valuable insights into the reaction
pathways and mechanisms of sorption reaction. Kinetics
describe the solute uptake rate that controls the residence time
of the sorbate uptake at the solid-solution interface, and are
important because to design appropriate sorption treatment
plants, the rate at which any pollutant is removed from aqueous
solution must be predicted [13]. In this work, experimental
data were fitted to first order, second order, pseudo first order,
pseudo second order, Elovich Boyd and intra- particle diffusion
models.
II. MATERIALS AND METHODS
A. Preparation of Activated Carbon
The spent grain used as one of the precursors was brought
from Nigeria breweries Ninth Mile Enugu. It was collected
immediately after use as a fresh spent grain. It was dried for 7
days under the sunlight to reduce the moisture content of the
grain and after which it was packed until use. The hamburger
seed shell was collected as a waste from Abakpa market,
Enugu, Enugu state Nigeria.
B. Adsorbate
Methylene Blue (MB) (C1. 52015) with empirical formular
C16H18N3SC1 and formular weight of 319.9g/mol was
supplied by De Cliff Integrated Ltd Ogbete Enugu, Enugu State
Nigeria (97% purity). It has maximum absorbance at
wavelength 661nm.
C. Preparation of Activated Carbon
The dried hamburger seed shell and spent grain were
crushed to desired mesh size (12 mm) and then carbonized at
800oC for 2 hrs in a stainless steel vertical tabular reactor
placed in a tube furnace. The char produced was crushed and
sieved with 600m sieve size. The char were soaked in 9M
KOH solution with (1.1.5) char to KOH ratio. The mixture
was then dehydrated in an oven at 105oC to remove moisture
and then was activated under the same condition as
carbonization, but to a different final temperature of 850oC for
1 hr. The activated products were then cooled to room
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temperature and washed with hot deionized water and 0.1NHcl
until pH of the washing solutions reached 6-7.
D. Adsorption Kinetic Model
The kinetic experiments were performed using a procedure
similar to the equilibrium studies. 50mls of known
concentration of MB was mixed with 0.02g of the adsorbent in
a flask. Then, the flask was agitated in a shaker incubator for a
contact time varied in the range 0- 240mins at a speed of
200rpm under room temperature. The adsorbent was separated
from the solution by centrifugation and the filtrate was
analyzed by the same procedure as batch equilibrium studies.
The amount of MB adsorbed at each time interval per unit mass
of the adsorbent, qt (mg/g), was calculated by equation 1:
(1)
Where Co (mg/L) is initial MB solution, Ct (mg/L) is its
concentration at time t, V (L) is the volume of the solution and
W (g) is the mass of the adsorbent.
The kinetics of methylene blue adsorption was analysed
using pseudo-first order model, pseudo-second order model,
and intra particle diffusion model.
E. Adsorption Isotherm
Batch isotherm studies were carried out in 250ml conical
flask at different temperature of 303K, 313K, 323K, 343K on
an Isothermal shaker for 6 hours to ensure equilibrium. 0.02g
of the adsorbent was mixed with 50ml of 30mg/l, 50mg/l,
80mg/l and 110mg/l of the solution at different pH of 4, 8 and
10. The pH was adjusted using 0.1M Hcl or 0.1M NaOH before
addition of the adsorbent. At the end of equilibrium time of 6
hours, the reaction mixture was centrifuged and the residual
MB concentration analysed. The amount of MB adsorbent at
equilibrium qe(mg/g) was calculated from the following
equation (2).
(2)
F. Adsorption Kinetic Model
The adsorption kinetic produces valuable information about
the reaction pathways and mechanism of the reactions. The
kinetic of methyleene blue adsorption was analysed using first
order model, pseudo-first order model, second order model,
pseudo-second order model, intra particle diffusion model,
Elovich model and Boyd model.
1) First order Model
The adsorption kinetics can be described by a simple first
order equation below:

Linearization gives

Where Cat (mg/l) is the concentration of MB at time t, Cao
(mg/l) is the initial concentration of MB. Ki is the rate constant
of first order adsorption (h 1) and t is the time gives in
minutes. A plot of log Cat versus t gives slope of and
intercept of LogCAo.
2) Pseudo First Order Model
The pseudo first order equation is generally expressed as:

Integrating and rearranging gives:

Where qe and qt are the amount of MB adsorbed (mg/g) at
equilibrium and at time t, respectively and Kpi is the rate
constant of pseudo-first order adsorption (min-1). A straight
lines will be obtained by plotting against t. the
values of the rate constant KI and qe were obtained from the
slopes and intercepts of the plot
3) Second order Model
The typical second order model equation is given as:

For the boundary condition of and
Integrating and rearranging gives

Where CAO and Cat are the initial concentration of MB
(Mg/l) and concentration at time t1 respectively. K2 is the rate
constant of the second order (min-1). A plot of
gives K2 and as slope and intercept respectively.
4) Pseudo Second order Equation
The pseudo second order adsorption kinetic rate equation is
expressed as:

Integrating for the boundary conditions



Which can be rearranged as follows:
and (10)
Where Kp2 is the rate constant of the pseudo second
equation (1/min) qe and qt are the sorption capacity at
equilibrium and time t (mg/l). h is the initial sorption rate. A
plot of t/qt versus (t) gives 1/qe and as slope and
intercept.
5) Intra Particle Diffusion Model
Weber-Morris found out that in many adsorption cases,
solute uptake varies almost proportionally with t rather than
with the contact time, t. the model is expressed as:

Where Kid is the intra particle diffusion rate constant
(mg/gh). Plotting qt versus t will give slope of kid and
intercept C (mg/g). Value of C gives the idea about the
thickness of boundary layer ie the larger the intercept, the
greater the contribution of the surface sorption in the rate
controlling step.
6) Elovich Model
The Elovich equation has been successfully applied to
represent chemisorptions processes and at low adsorption rate.
The equation is as follows:
(11)
Integrating with suitable boundary conditions gives:

Where x is the initial sorption rate constant (mg/gml), and
parameter is related to the extent of the surface coverage and
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to the activation energy of chemisorptions (g/mg). The constant
can be obtained from the plot of qt versus Lnt as the slope and
the intercept. The correlation coefficients were better but still
lower than that of pseudo second order model.
7) Boyd Model
In order to determine the actual rate controlling step
involved in sorption process, Boyd model is used which is as
follows:

Where F is the fractional attainment of equilibrium at time
t, and is obtained by the expression: where
qt(mg/g) is the amount of sorbate taken up at time t, and qe
(mg/g) is the maximum equilibrium uptake and


is time constant (min-1) of the sorbent particle (cm),
assumed to be spherical and m is an integer that defined the
finite solution hence, is given by the equation

Thus, the value of can be computed for each value of F1
and then plotted against time, t.
G. Adsorption isotherm Models
Adsorption isotherm equations are models describe
experimental sorption data. It helps to understand the nature of
the interaction between the adsorbate and adsorbent used for
the adsorption. An adsorption isotherm describes the
relationship between the amount of adsorbate uptaken by the
adsorbent and the adsorbate concentration remained in the
solution [14], [15]. The equation parameter and the underlying
thermodynamic assumptions of these equilibrium models often
provide some insight into the adsorption mechanism, the
surface properties of an adsorbent and affinity of the adsobate
for an adsorbate [16], [15], [17], [18]. In this study, the
experimental results were fitted to langmuir, freudlich, Temken
Dubinin Radush Kevich Isotherms.
1) Langmuir Isotherm
The Langmuir adsorption isotherm describes quantitatively
the build-up of a layer of molecules on an adsorbent surface as
a function of the concentration of the adsorbed material in the
liquid in which it is in contact [19]. This isotherm is based on
the assumption that the adsorption process takes place at
specific homogenous sites within the adsorbent surface and that
once a dye molecule occupies a site, no further adsorption can
take place at that site which concluded that the adsorption
process is monolayer in nature [18]. The isotherm can be
written as:

The linear form of the isotherm is given as:

(16)
Where qe is the amount of adsorbate adsorbed per gram of
the adsorbent (mg/g), CAe is the concentration of adsorbate in
liquid equilibrium, (mg/l). the constant KL and qo relate to
energy of adsorption and maximum adsorption capacity
respectively. KL is a measure of heat of adsorption utilized to
calculate dimensionless separation parameter KL qo is in mg/g.
To determine if the adsorption process is favourable or
unfavourable, for the Langmuir type adsorption process, the
isotherm shape can be classified by a term RL a
dimensionless constant separation factor which is defined as
below [20].

(17)
Where KL(L/mg) is the Langmuir constant and Cao is the
lowest initial solute concentration (mg/l). a plot of Cao / qe
versus CAe from the linear relationship of the model will give

and 1/qo as intercept and slope respectively.
2) Freundlich Isotherm
The Freundlich Isotherm equation is based on the
assumption that the adsorbent has a heterogeneous surface
composed of different classes of adsorption site [21]. This
isotherm does not predict any saturation of the sorbent by the
sorbate, indicating multilayer sorption of the surfaces [22]. The
Freundlich isotherm is expressed by the following equation.

(18)
A linear form of the freundlich can be obtained by taking
the logarithm to the above equation.

(19)
Where KF = freundlich constant. Where KF (mg/g) is the
constant related to the adsorption capacity. The value of 1/n
ranging between 0 and 1 is a measure of adsorption intensity or
surface heterogeneity, becoming more heterogenous as its
value gets closer to zero [23]. A plot of Logqe versus CAe will
give intercept as LogKF and slope as 1/n.
3) Temkin Isotherm Model
The heat of the adsorption and the adsorbate adsorbate
interactions in a adsorption process were studied by Temkin
and Pyzhev [24], and its equation is given as follows:

(20)
Where T is the absolute temperature in K and R is the
universal gas constant 8.3143J/molk. The constant b is related
to the heat of adsorption qe(mg/g) and Ce(mg/l) and the
equilibrium concentration respectively. A and B are constants
related to adsorption capacity and intensity of adsorption. A
plot of qe versus Ince yields a slope of B and intercept of BlnA.
4) Dubinin Raduschkevich (D R)
Dubinin Radushkevich model is similar to the Langmuir
model but does not assume a homogenous surface or constant
energy potential [21]. The D R equation can be written as:
) (21)
Where is the Polanyi potential (J/mol) given by:

Linearizing it gives

Where qe is the amount of sorbate adsorbed at equilibrium
(mg/g), qmax is the theoretical saturation capacity (mg/g), BD
is a constant related to the adsorption capacity (mg2/l2). A plot
of Lng versus (RTLn(1 + 1/Ce) yields a straight line with a
slope of -2BD and intercept of Lnqmax. The value of BD can
be used to calculate the sorption mean free energy E (KJ/Mol).

-1/2

Taking the logarithm of the D R equation, it becomes

(22)
A plot of Lnqe against gives slope of -2BD and intercept
of Lnqmax.
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III. RESULTS AND DISCUSSION
KINETIC EQUATION pH KINETIC PARAMETERS R
2

First Order Kinetics 2
4
6
8
10
K1 = -0.0046 (min
-1
)
K1 = -0.0046 (min
-1
)
K1 = -0.0069 (min
-1
)
K1 = -0.0069(min
-1
)
K1 = -0.0046 (min
-1
)
0.796
0.739
0.797
0.887
0.796
Second order Model 2
4
6
8
10
K2 = 0
K2 = 0.003
K2 = 0.017
K2 = 0.039
K2 = 0.020
0.852
0.852
0.871
0.904
0.876
Intra Particle Diffusion Model 2
4
6
8
10
Kid = 1.9267 (min
-1
), C = 38.917
Kid = 0.5807 (min
-1
), C = 65.187
Kid = 0.3089 (min
-1
), C = 70.297
Kid = 0.0986 (min
-1
), C = 73.352
Kid = 0.0919 (min
-1
), C = 73.362
0.8365
0.7186
0.8198
0.8959
0.822
Elovch Model 2
4
6
8
10
= 0.108g/mg, = 16.145mg/g.min
= 0.351g/mg, = 2.992mg/g.min
= 0.693g/mg, = 1.474mg/g.min
= 2.288g/mg, = 0.439mg/g.min
= 2.273g/mg, = 0.442mg/g.min
0.941
0.861
0.887
0.874
0.936
KINETIC EQUATION INTERCEPT R
2

Boyd Model 2
4
6
8
10
-0.165
1.372
1.813
2.837
3.208
0.972
0.961
0.929
0.873
0.976
TABLE 1. KINETICS PARAMETERS

Pseudo First order Pseudo Second order
pH Quexp(mg/g) Qualc(mg/g) K1(min
-2)
R
2
IKP2(min
-1
) H Qe(mg/g) R
2

2
4
6
8
10
64.549
72.687
74.3575
74.7223
74.5688
20.09
3.313
1.5922
0.5688
0.3515
0.0161
0.0092
0.0046
0.0023
0
0.767
0.364
0.132
0.030
0.006
KP2= 0.001
KP2= 0.005
KP3= 0.009
KP3= 0.024
KP3= 0.034
5.102
29.586
53.28
42.012
201.183
71.429
76.923
76.923
76.923
76.923
0.998
1.0
1.0
1.0
1.0
TABLE 2. KINETICS PARAMETERS

A. Kinetics models
The study of sorption kinetics in wastewater treatment is
significant as it provides valuable insights into the reaction
pathways and mechanisms of sorption reaction
1) First order kinetics
In order to determine the controlling mechanism of
adsorption process such as transfer and chemical reaction, the
first order kinetic model was used to test the experimental data.
The values of rate constant were calculated from the slopes of
the graphs plotted and they are presented in table (1). The low
correlation coefficient (R2) obtained at different pH values
showed poor agreement of the first order model with the
experimental data.
2) Pseudo-first order
The pseudo-first order parameters at different pH along side
with their correlation coefficients (R2) are shown in table (2).
The R2 values obtained were small at all the pH studied, and
the experimental qe values did not agree with the calculated
values obtained from the linear plots (table 2).
3) Second order model
The values of the correlation coefficients, were relatively
small compared to the pseudo second order meaning that the
model did not fit the experimental values well.
4) Pseudo second order
The values of qe and K were obtained from the slope and
intercept. The values of the rate constants, correlation
coefficients, the experimental and calculated values are shown
in table 2.
It can be seen that the correlation coefficients for the linear
plot of the pseudo second order increased from 0.988 to 1 as
the pH increased, which is higher than the correlation
coefficients of all other models studied. Also, there is a good
agreement between the experimental qe values and the
calculated qe values. This indicates that the adsorption kinetic
is better represented by the pseudo-second order model. The
high initial sorption rate, h, obtained showed that the adsorption
was rapid. The uptake of adsorbate by adsorbent has been
observed to occur in two stages: the first rapid and
quantitatively predominant and the second slower and
quantitatively insignificant [25], [26]. The rapid adsorption of
MB by this adsorbent is probably due to the abundant
availability of active sites on the biomass, and the perceived
porous and mesh structure of the adsorbent which provides
ready access and large surface area for the adsorption of MB
dye on the binding sites [27], [28].
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100 | P a g e








Fig. 1. Kinetics plots
5) Intra particle diffusion
The intra particle diffusion model was proposed to identify
the adsorption mechanism and to predict the rate controlling
step. The intra particle diffusion model usually includes three
steps. The first portion is the external surface adsorption or
boundary layer diffusion. The second portion is the gradual
stage of adsorption which is the intra particle diffusion. If the
plot of qt versus t1/2 is linear and passed through the origin,
then the intraparticle diffusion is the rate-controlling step [29].
The third portion is the final equilibrium stage in which the
intra particle diffusion starts to slow down due to the extremely
low dye concentration left in the solution [28].
The plot shows that the linear plot did not pass through the
origin whichindicated that the intra particle diffusion was not
only the rate controlling step and the boundary layer diffusion
controlled the adsorption to some extent [48]. This deviation
may be due to the difference in mass transfer rate in the initial
and final stage of adsorption [29], [30].
The values of C and Kid are given in Table 1. The values of
the intercept C increased with an increase in pH, which showed
that boundary layer effect increased as pH increases.
The correlation coefficients for intraparticle diffusion were
lower than that for the pseudo second order kinetics which
showed that the present system may be followed by
intraparticle diffusion, but is not the only rate controlling step.
6) Boyd model
A linear plot of Bt against t, passing through the origin
implies that pore-diffusion controls the rate of mass transfer.
However, if the plot is non linear or linear but does not pass
through the origin film-diffusion or chemical reaction dominate
the adsorption rate [31], [32], [33].
Boyd model was used to investigate the contribution of film
resistance to the kinetics of MB sorption. The model assumes
that the main resistance to diffusion is the boundary layer
surrounding the adsorbent particle.
The latter seems to be the case in MB adsorption on the
composite adsorbent as shown in figure. However, it seems the
pore diffusion becomes more important at lower pH, as the
intercept approaches O with decrease in pH as indicated on
table (1). The correlation coefficient is equally reasonable, but
still, they are lower than that of pseudo second order model.
B. Isotherm models
An adsorption isotherm is an invaluable curve describing
the phenomenon governing the retention (or release) or
mobility of a substance from the aqueous porous media or
aquatic environments to a solid phase at a constant temperature
and pH .
1) Langmuir
The value of the separation factor (RL) indicates the nature
of adsorption process. RL values indicates the type to be
irreversible (RL = 0), favourable (0< RL <1), linear (RL = 1) or
unfavourable (RL > 1). The linear plot of ce/qe vs ce indicated
the applicability of Langmuir adsorption isotherm.
Consequently, suggested the formation of mono layer coverage
of the adsorbate on the surface of the adsorbent [34]. Langmuir
constants, qo and KL were calculated from the slopes and
intercepts are given in table 3 along with the correlation
coefficient (R2) and separation factor (RL). From the table, it is
clear that the KL values were higher at higher temperature,
which showed endothermic nature of MB adsorption. The
average values of RL for each of the temperature and pH used
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were between 0 and 1, which indicated the favourable
adsorption of MB. This was in agreement with the work done
by Dalia Khalid et al on the batch adsorption of basic dye using
acid treated kenaf fiber [29], work done by Emad N. ElQada et
al in adsorption of methylene blue into activated carbon form
[35], I.A.W Tan et al on equilibrium and kinetic studies on
basic dye adsorption by oil palm fibre activated carbon [36] etc.
2) Freundlich isotherm
The values of Freundlich constants and correlation
coefficients (R2) are given in table 3. The values of Kf and n
changed with the rise in temperature. The value of n showed an
indication of the favourability of adsorption. Values of n larger
than 1, showed the favourable nature of the adsorbent [34],
[37], [38]. The value of n suggested that MB was favourably
adsorbed by the activated carbon prepared from Hamburger
seed shells. The correlation coefficients greater than 0.980
showed that the data fitted well with Freudlich equation was
statistically confirmed by giving greater R2 values closer to
unity (0.85 0.999). This implies that Freudlich model may
better describes an adsorption isotherm for the adsorbent. This
adsorptive behaviour indicates that the adsorption takes place
on a heterogeneous surface, which may be attributed to the
various active sites on the adsorbent [39]. This was in line with
the work done by Hui Deng et al on adsorption of methylene
blue in adsorbent materials produced from cotton stalk [40].






Fig. 2. Isotherm plots
3) Temkin isotherm
The linear isotherm constants and coefficients of
determination are presented in table 4. It shows that the
equilibrium binding constant (A) (l/mg) which corresponds to
the maximum binding energy increased with increase in
temperature and was maximum at pH of 10. The constant b
which is related to the heat of adsorption, equally increased
with increase in temperature. The results implied that the
affinity of the binding sites for MB increased with increase in
temperature. Examination of the data shows that the Tempkin
Isotherm is applicable to the MB adsorption onto hamburger
activated carbon judged by high correlation coefficient (R2
ranged from 0.915 to 0.985).
TEMPERATURE LANGMUIR CONSTANT FREUNDLICH CONSTANT
TEMP(K) qo(mg/g) KL(L/mg) RL R
2

1
/n n KF R
2

303 pH4 0
pH10 500
0
1.0
1.0
0.032
0.997
0.923
0.859
0.517
1.164
1.934
78.7
185.35
0.999
0.989
313 pH4 1000
pH10 500
0.25
2.0
0.118
0.016
0.701
0.950
0.765
0.501
1.307
1.938
164.8
198.6
0.987
0.994
323 pH4 500
pH10 500
1.0
2.0
0.032
0.016
0.933
0.980
0.652
0.516
1.534
1.980
193.2
221.8
0.997
0.990
333 pH4 500
pH10 500
1.0
2.0
0.032
0.016
0.991
0.967
0.608
0.505
1.645
1.996
213.8
251.2
0.985
0.997
TABLE 3: ISOTHERM CONSTANTS FOR MB ADSORPTION ON COMPOSITE ADSORBENT

TEMKIN CONSTANT DUBININRADUSHKEVICH CONSTANT
B A b R
2
Qm(mg/g) BD E(KJ/mol) R
2

303 pH4 126.5
pH10 76.23
1.8
13.6
19.9
33.0
0.976
0.924
421.6
333.6
5 x10
-4

15 x 10
-4

3.1..6
5.7.7
0.986
0.951
313 pH4 112.1
pH10 74.55
5.1
16.6
23.2
34.9
0.915
0.946
435.3
343.8
2.5 x 10
-4

1.5 x 10
-4

4.472
05.77
0.958
0.972
323 pH4 97.16
pH10 77.85
8.3
18.4
27.6
34.9
0.954
0.967
411.6
376.2
2 x 10
-4

1.5 x 10
-4

5.0.0
5.777
0.979
0.984
333 pH4 92.87
pH10 75.83
10.9
25.3
29.8
36.5
0.985
0.951
428.8
389.2
1.5 x 10
-4

1 x 10
-4

5.77
7.0.7
0.994
0.926
TABLE 4: THERMODYNAMIC PARAMETER FOR MB ADSORPTION AT PH4



International Journal of Technical Research and Applications e-ISSN: 2320-8163,
www.ijtra.com Volume 2, Issue 4 (July-Aug 2014), PP. 96-103
102 | P a g e

Concentrations (mg/ls) G(KJ/mol) P
o
H(KJ/mol) S(Jmol
-1
K
-1
)
30
o
C 40
o
C 50
o
C 60
o
C
30mg/l -11.556 -13.410 -15.264 -17.118 44.621 0.1854
50mg/l -11.221 -12.844 -14.468 -16.092 37.978 0.1624
80mg/l -11.009 -12.538 -14.067 -15.596 35.318 0.1529
110mg/l -11.104 -12.283 -13.461 -14.640 24.618 0.1170
AT pH10
Concentrations (mg/ls) G(KJ/mol) H(KJ/mol) S(Jmol
-1
K
-1
)
30
o
C 40
o
C 50
o
C 60
o
C
30mg/l -15.424 -16.464 -17.504 -18.544 16.088 0.104
50mg/l -13.642 -14.652 -15.662 -16.672 16.961 0.101
80mg/l -12.827 -13.947 -15.067 -16.187 21.109 0.112
110mg/l -12.395 -13.225 -14.055 -14.885 12.754 0.083

4) Dubinin-radushkevich model
The Langmuir Isotherm constants do not give any
information concerning the chemical or physical properties of
the sorption. But the calculated sorption mean free energy E,
from the D-R isotherm gives information about the chemical or
physical properties of the sorption [19]. The values of the mean
adsorption energy that is less than 8kj/mol, revealed that the
adsorption of MB was predominantly a physical process rather
than a chemical one [37], [41]. The correlation coefficient of
the isotherm showed that D-R equation represents a good fit of
the experimental data (Table 4).
Moreover, the maximum adsorption capacity qm obtained
using D-R isotherm for adsorption of MB is 435.3mg/g, which
is close to half of that obtained (1000mg/g) from Langmuir
isotherm model (Table 4).
C. Adsorption thermodynamics
The thermodynamic parameters of the adsorption process
were determined from the Vant Hoff equation by plotting
lnKD versus 1/T for different temperature at 303,313, 323 and
333K as follows:
Go = H TS (23)
LnKc = -H/RT + S/R (24)
Where Kc is the equilibrium constant, which is the ratio of
the equilibrium concentration of the dye ion on the adsorbent to
the equilibrium concentration of the dye ions in solution. R is
the universal gas constant (8.314J/kmol), T (k) is the absolute
temperature. H represents the difference in binding energies
between the adsorbent and the adsorbate (solute) and between
the solvent and the solute.
The values of S
o
and H
o
were obtained from intercept
and slope respectively of plot of LnKc against I/T.
The negative values of G
o
(table 5) indicated the
feasibility of the process and the spontaneous nature of the
adsorption. The value of G
o
became more negative with
increasing temperature. This showed that increase in
temperature was favourable for the removal process. The
results also showed that both enthalpy and entropy values were
positive at different concentration, signifying that the
adsorption process was endothermic and the degree of
dispersion increased with increase in temperature. The
endothermic behaviour observed from enthalpy value further
confirmed the trend of adsorption of MB on the adsorbents
which were found to increase as temperature was increased.
The nature of the adsorption process was confirmed by the
magnitude of the H
o
values. It is accepted that if magnitude of
enthalpy change is less than 84Kj/mol, adsorption is physical,
however, chemisorptions takes place from 84 to 420Kj/mol.
The range of values of H
o
from table 5 showed that the nature
of adsorption is physical.
IV. CONCLUSION
The composite activated carbon used for this study was
prepared from brewers spent grain and sea bean shell at a ratio
of 1:1. The result of this study can be summarized as follows;
The developed composite activated carbon is a
promising adsorbent for removal of cationic dye from
solution.
The experimental data showed perfect fit with the
Freundlich isotherm, which confirm that the
adsorption process is heterogeneous, non- specific and
non-uniform in nature. Therefore, the mechanism of
adsorbate-adsorbent interaction is complicated
involving a wide range of sites differing in a number
of aspects including energy considerations.
The kinetic study was investigated using first order,
pseudo first order, second order, pseudo second order,
Elovich, Boyd and intra-particle diffusion models.
The result indicates that adsorption kinetics followed
the pseudo second order with the intra- particle
diffusion model as one of the rate limiting step.
The sorption process was found to be endothermic in
nature with negative value of the entropy.
The negative value of the Gibbs free energy and
positive value of the enthalpy suggested the
adsorption to occur by physical process.
V. ACKNOWLEDGEMENTS
The authors wish to thank PYMOTECH RESEARCH
CENTRE AND LABORATORIES ENUGU, ENUGU STATE
NIGERIA for all their facilities used throughout the research
work.
REFERENCES
[1] J. W. Lee, S. P. Choi, R. Thiruvenkata Chari, W. G. Shim, H.
Moon, Evaluation of the performance of adsorption and
coagulation processes for the maximum removal of reactive
dyes, dyes pigments 69 (2006), 196-203.
[2] I. A. W. Tan, A. L. Ahmad, B. H. Hameed. Optimization of
preparation conditions for activated carbons from coconut husk
using response surface methodology, Chemical Engineering
Jornal, 137 (2008) 462-470.
International Journal of Technical Research and Applications e-ISSN: 2320-8163,
www.ijtra.com Volume 2, Issue 4 (July-Aug 2014), PP. 96-103
103 | P a g e

[3] Emad N. ElQada, Stehen J. Allen, Gavin M. Walker. Adsorption
of methylene blue onto activated carbon produced from steam
activated bituminous coal. A study of equilibrium adsorption
isotherm. Chemical Eng. Journal 124 (2006) 103-110.
[4] A. Damirbas, Agricultural based activated carbons for the
removal of dyes from aqueous solutions: a review, J. Hazard
Mater., 167 (2009) 1-9
[5] Dalia Khalid Mahmoud, Mohamed Amran Mohd Salleh, Wan
Azlina Wan Abdul Karim, Azni Idris, Zurina Zainal Abidin,
Batch adsorption of basic dye using acid treated kenaf fiber char:
Equilibrium, Kinetics and thermodynamic studies. Chemical
Engineering Journal 181-182 (2012) 449-457.
[6] Emmanuel, I. Unuabonah, Gilbert U. Adie, Lora O. Onah,
Olalere G. Adeyemi. Multistage optimization of the adsorption
of methylene blue dye defatted carica papaya seeds. Chemical
Engineering Journal 155 (2009) 567-579.
[7] M. T. Sulak, E. Demorbas, M. Kobya, removal of Astrazon
yellow 7GL from aqueous solutions by adsorption onto wheat
bran, Bioresour. Technol. 98 (2007) 2590-2598.
[8] R. Qadeer, Adsorption behavior of ruthenium ions on activated
charcoal fron nitric acid medium, Colloids surf, A 293 (2007)
217-223.
[9] K. Vasanth Kumar, S. Sivenesan. Isotherm parameters for basic
dye onto activated carbon. Comparison of linear and non-linear
methods. Journal of Hazardous materials B 13 (129), PP. 147-
150.
[10] K. Y. Foo, B. H. Hameed. Insight into the modeling of
adsorption isotherm systems. Chemical Engineering Journal 156
(2010) 2-10.
[11] G. Limousin, J.P Gaudet, L.Charlet, S. Szenknect, V. Barthens,
M. Krimissa, Sorption Isotherm: a review on physical bases,
modeling and measurements. Appl. Geochem. 22(2007) 249-
275.
[12] S. J. Allen, G. Mckay, J. F. Porter, Adsorption isotherm models
for basic dye adsorption by peat in single and binary components
systems. J. Colloid interface Sci. 280 (2004) 322-333.
[13] Yuh-Shan Ho, Chun Chiao, Chiang and Yung Cheien Hsu.
Sorption kinetics for dye removal from aqueous solution using
activated clay. Separation science and Technology. 36 (11),
2473-2488 (2001)
[14] M.S. Chiou, H.Y.Li. Equilibrium and Kinetic Modeling of
Adsorption of Reactive Dye on Cross Linked Chitosan Beads, J.
Hazard Mater. 93, 2002, pp.233 -248.
[15] I. Langmur. Adsorption of Gases on Plane Surface of Glass,
Mica and Platinum, J. AM. Chem. Soc. 40, 1981, pp. 1361-
1403.
[16] I. Langmur, The Constitution and Fundamental Properties of
Solids and Liquids. J. AM-Chem-Soc 38, 1916, pp.2221 - 2295.
[17] O. Abdel Washab. Evaluation of the Use of Loofa Activated
carbon as Potential Adsorbents for Aqueous Solutions
Containing Dye, Desalination 222, 2008, pp.357-367.
[18] M. Ghaedi, B. Sadeghian, A. Amiri Pebdan, R. Sahraei, A.
Daneshfar and C. Duran. Kinetics, Thermodynamics and
Equilibrium Evaluation of Direct Yellow 12 Removal by
Adsorption onto Silver Nanopartarticles Loaded Activated
Carbon. Chemical Engineering Journal 187, 2012, pp.133-141.
[19] Naseen rauf, S.S. Tahir, Jung-Ho Kang, Yoo-Seok Chan.
Equilibrium, Thermodynamics and Kinetics Studies for the
Removal of Alpha and Beta Endosulfan by Adsorption onto
Bentonite Clay. Chemical Engineering Journal. 2012
[20] E. Malkoc, Y. Nuhoglu. Determination of kinetic and Equilirium
Parameters of the Batch Adsoprtion of Cr (VI) onto Waste
Acorn of Quercus Ithaburensis, Chemical Eng. Process. 46,
2007, pp.1020-1029.
[21] Agustin Marsal, Fernado Maldonado, Sara Cuadros, M. Elena
Bautista, Albert, M. Manich. Adsorption Isotherm,
Thermodynamics and Kinetic Studies of Poly phenols onto
Tannery Shavings. Chemical Eng. Journal, 183, 2012, pp.21
29.
[22] R. Donat, A. Akdogan, E. Erdem, H. Cetisli. Thermodynamics
of Pb (+2) and Ni(+2) Adsorption onto Natural Bentonite from
Aqueous Solutions. J. Colloid Interf. Sci. 286, 2005, pp.43 52.
[23] E. Zeynep, N.A. Filiz. Equilibrium and kinetic Mechanism for
Reactive Black 5 Sorption onto high Lime Soda Fly Ash. J.
hazard mater. 143, 2007, pp.226 232.
[24] M.J. Temken, V. Pyzhev. Recent Modification to Langmuir
Isotherms. Acta Physiochim USSR 12, 1940, pp.217-222.
[25] M. Auta, B.H. Hameed. Odified Mesoporous Clay Adsorbent for
Adsorption isotherm and Kinetics of methylene Blue. 198-199,
2012, pp.219-227.
[26] Y.T. Sag, Kutsal. Fully Competitive Biosorption of Chromium
(VI) and Iron (II) Ions from Binary Metal Mixtures by R.
Arrhizus: Use of the Competitive Langmuir Model, process
Biochern. 31, 1996, pp. 561-579.
[27] W.H. Cheung, Y.S. Szeto, G. Mckay. Intraparticle Diffusion
Processes During Acid Dye Adsorption onto Chitosan,
Bioresour. Technol. 98, 2007, pp.2897 2904.
[28] Dalia Khalid Maamoud, Mohaamad Amran Mohasalleh, Wan
Azlina Wari Abdul Karima, Azni Idris and Zurina Zainal
Abidin. Batch Adsorption of Basic Dye using Acid treated
Kenaf Fibre Char: Equilibrium, Kinetic and Thermodynamic
Studies. Chemical Engineering Journal 181, 2012, pp.449 457.
[29] B.H. Hameed, H. Hakimi. Utilization of Clurian (Durio
Zibethinus Murray) Peel as Low Cost Sorbent for the Removal
of Acid Dye from Aqueous Solutions. Biochem. Engineering
Journal 39, 2008, pp.338 343.
[30] Mehmet Ulas Dural, Levent Cakas, Sergios K. Papagergiou and
Fotis K. Katsaros. Methylene Blue Adsorption on Activated
Carbon Prepared from Posidonia Oceanica (L) Dead Leaves:
Kinetics and Equilibrium Studies. Chemical Engineering Journal
168, 2011, pp.77 85.
[31] G.E. Boyd, A.W. Adamsum, L.S. Myers Jr. The Exchange
Adsorption of Ions from Aqueous Solutions by organic Zeolites
(II) Kintics. J. AM. Chem. Soc. 67, 1947, pp.2836 2848.
[32] D. Reichenberg. Properties of Ion Exchange Resins in Relations
to their Structure III. Kinetics of Exchange, J. AM. Chem. SOC.
75, 1953, pp.589 598.
[33] Z.A. Al-Othman, R. Ali and Mu. Navshat. Hexa Valent
Chroimium Removal from Aqeuous medium by Activated
carbon Prepared from peanut Shell: Adsorption Kinetics,
Equilibrium and Thermodynamic Studies. Chemical Engineering
Journal 184, 2012, pp.238 247.
[34] Emad N. El Qada, Stephen J. Allen, Gavin, M. Walker.
Adsorption of Methylene Blue unto Activated Carbon Produced
from Steam Activated Bituminous Coal: A Study of Equilirium
Adsorption Isotherm. Chemical Engineering Journal 124, 2006,
pp. 103 110.
[35] I.A.W. Tan, B.H. Hameed and A.L. Ahmed. Equilibrium and
Kinetic Studies on basic Dye Adsorption by Oil Palm Fibre
Activated carbon. Chemical Engineering Journal 127, 2007, pp.
111-119.
[36] N. Daneshur, D. Salari, S. Aber. Chromium Adsorption and
Cr(V) Reduction to Tribalent Chromium in Aqueous Solutions
by Soya Cake. J. Hazard Mater, 94, 2002, pp.49 61.
[37] P.K. Malik. Dye Removal from Wastewater Using Activated
Carbon Developed from Sawdust: Adsorption Equilibrium and
Kinetics. J. Hazard, mater, 113, 2004, pp.81 88.
[38] Vipasiri Vimonses, Shaomin Lei, Bo Jin, Chris W.K. Chow and
Chris Sant. Kinetic Study and Equilibrium Isotherm Analysis of
Congo Red Adsorption by Clay Materials. Chemical
Engineering Journal 148, 2009, pp. 354 364.
[39] Hui Deng, Jianjang, Lu, Guoxue LI, Genli Zhang and Xugen
Wang. Adsorption of Methylene Blue on Adsorbent Materials
produced from Cotton Stalk. Chemical Engineering Journal 172,
2011, pp. 326-334.
A.H. Chen, S.M. Chen. Biosorption of Azo Dyes from Aqueous
Solution by Glutaraldehyde Cross linked Chitosans, J. Hazard
Mater 172, 2009, pp.1111 1121.