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Kinetics and equilibrium studies of adsorption of phenol in aqueous solution onto activated carbon prepared from rice
and coffee husks
water to eliminate the impurities and then dried in the sun for starch as indicator until a clear solution was observed.
72 hours before activation.
The ratio of impregnation is defined as the ratio of the mass - Batch Adsorption
of the activating agent to the mass of the dry biomass Adsorption experiments were carried out by mechanical
precursor. The washed rice husk was impregnated using the agitation at room temperature. For each run, 20 mL of phenol
above ratio. To produce an activated carbon with an of known initial concentration (between 50-110 mg/L) was
impregnation ration of 75%, 20 g of dried rice husk was put in treated with a known weight of different activated carbon.
contact with 35 g of a solution of H3PO4 of concentration 1M. After agitation for the appropriate length of time, the solution
The mixture was allowed for 30 minutes for activation to take was filtered, and the filtrate analyzed to obtain the
place before being dried in an oven set at 105C for 24 hours. concentration residual phenol by using the UV/Vis
The samples of impregnated rice husk were carbonized for 1 spectrophotometer (Jenway model 6715). Similar
hour at 450C and 500C, at a heating rate of 5C/min. The measurements were carried out by varying adsorbent doses,
products obtained from the calcination were washed with pH of the solution, and the initial concentrations of the
distilled water until there were no phosphate ions detected any solution. The percentage removal (%R) of phenol and the
more in the water when tested with lead nitrate. The activated amount (Qe) of phenol adsorbed were calculated using the
carbons obtained were labeled CAH1 obtained from rice husk following expressions:
at 500C; CAH2 obtained from rice husk at 450C; and (2)
CAMH obtained at 500C by mixing 12 g of rice husk with 8
g of coffee husk. The experimental setup used is an ISUNU (3)
mark electric furnace with automatic regulation, having the
temperature programmer relied to the furnace. The various
activated carbons thus obtained were dried for 24 hours at the Co is the initial concentration of the phenol, Ce is its
temperature of 105C, before being crushed and filtered to equilibrium concentration, Ct is the concentration of the
obtain activated carbon of particles of size lower than 100 phenol solution at the time t, V is the volume of the solution,
m. and m is the mass of the absorbent.
167 www.erpublication.org
International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-10, October 2014
After integration and applying boundary conditions at t = 0, the adsorbent mass. Equilibrium data were then fitted by using
= 0; and at t = t, = , the integrated form of equation the isotherm Langmuir, Freundlich, Elovich and Temkin.
(4) becomes: The Langmuir Isotherm
ln ( = ln - (5) The Langmuir adsorption isotherm is often used of the
equilibrium of the adsorption of solutes from solutions. It is
expressed as [20]:
The pseudo-second order model:
(14)
The pseudo-second order chemisorption kinetic
equation (Ho and Mckay) [15] is expressed as Equation 6:
(6) Where, Qe is the adsorption capacity at the equilibrium
solute concentration, in the mg of adsorbate per g of
Where and are the adsorption capacity (mg/g) at adsorbent; Ce is the equilibrium concentration of adsorbate in
equilibrium, and at time t, respectively and is the rate solution (mg/L), while Qm is the maximum adsorption
constant for the pseudo-second order adsorption (g/mg.min). capacity corresponding to complete monolayer coverage
For boundary conditions at t = 0, qt = 0; expressed in mg of solute adsorbed per g of adsorbent. K L is
and at t = t, = , the integrated and rearranged form of the Langmuir constant in L of adsorbate per mg of adsorbent,
and it is related to the energy of adsorption. Equation (14) can
equation (6) is:
be rearranged in the linear form:
(7)
(15)
The Elovich kinetic equation
The Elovich equation is generally expressed as [16]:
The factor of separation of Langmuir, RL, which is an
(8) essential factor characteristic of this isotherm is calculated by
Where is the sorption capacity at time t (mg/g), is the using the relation [21]:
initial adsorption rate (mg/g.min), and is the desorption rate (16)
constant (mg/g.min) during any one experiment.
Where C0 is the higher initial concentration of methyl
The integrated and simplified equation
orange, while KL and Qm are the Langmuir constant and the
(assuming that t 1) is:
maximum adsorption capacity respectively. The parameters
(9) indicate the shape of isotherm as follows:
Intraparticle diffusion model RL values indicate the type of isotherm: to be irreversible
The rate of adsorption is known to be controlled by several (RL = 0), favorable (0 < RL < 1), linear (RL = 1), or
factors including the following [17]: unfavourable (RL> 1).
Diffusion of solute from the solution to the film The Freundlich Isotherm
surrounding the adsorbent particle; The Freundlich isotherm is based on adsorption on a
Diffusion through the film to the particle surface; heterogeneous surface, and it is expressed as [22]
Diffusion from the particle surface to the internal sites on Qe = FCe1/n (17)
the adsorbent particle; Where Qe is the quantity of solute adsorbed at equilibrium,
Uptake of solute on the solute surface, and this could also called adsorption density; it is expressed in mg of
involve several mechanisms such as physicochemical adsorbate per g of adsorbent; Ce is the concentration of
sorption, ion exchange, complexation or precipitation. adsorbate at equilibrium, F and n are empirical constants. By
One type of equation used to model the intraparticle taking logarithms on both sides, the equation gives the more
diffusion was developed using the concept of linear driving convenient linear form:
force. It is expressed as [18], [19]: (18)
(10)
Xi is the boundary layer diffusion effect, and it depicts the The Temkin Isotherm
boundary layer thickness, while K1 is the initial rate of The isotherm of Temkin developed in 1941 for an
adsorption (mg/g.min), and it is controlled by intra-particle adsorption in gas phase was transposed to the liquid phase by
diffusivity. Zarrouki in 1990 [23]. The isotherm of Temkin was generally
presented by the following equation:
(19)
Batch equilibrium experiments
For each run, the adsorbent was mixed with 20 mL
Where is the rate of covering of the surface of
solution of dye at different initial concentrations from 50-110
mg/L. The suspension was stirred for 60 minutes with the adsorbent, is the constant of balance and is the
different activated carbon. The amount of dye adsorbed at variation of the energy of adsorption. The linear form of the
equilibrium, Qe (mg/g) was calculated using equation (2): equation of Temkin is:
(3) (20)
Where, C0 and Ct are the initial and equilibrium The value of which one introduces into this degree of
concentrations of phenol, V the volume of the solution, and m covering is given starting from the equation of Langmuir.
168 www.erpublication.org
Kinetics and equilibrium studies of adsorption of phenol in aqueous solution onto activated carbon prepared from rice
and coffee husks
The Elovich isotherm presence of attracting groups of electrons tends to attract the
This isotherm differs from that of Langmuir about the electrons of the -systems in carbon. interaction is usually
evolution of the sites of adsorption. The number of site the mean mechanism involved in phenol adsorption. The
available varies in this model in an exponential way during maximum quantities adsorbed in equilibrium are 8.56, 8.68
adsorption, which implies an adsorption in several layers. The and 9.56 mg/g respectively for CAH1, CAH2 and CAMH
Elovich isotherm is described by the relation [19]: leading to a percentage of 64.46, 66 and 72.91%.
The elemental analysis of rice husk and activated carbon Adsorbent Bulk Moisture pH pHpcz
are listed in table 2. The results show that the quantities of density Content
element decreases when the temperature of activation (kg/m3) (%)
increases. These is in accordance with the volatile matters like
CO, CO2, CH4, aldehydes, and so forth. CAH1 802 8.86 5.20 3.0
169 www.erpublication.org
International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-10, October 2014
170 www.erpublication.org
Kinetics and equilibrium studies of adsorption of phenol in aqueous solution onto activated carbon prepared from rice
and coffee husks
Figure 5: Linearized pseudo-second order plots Figure 7: Linear plot of the model of Langmuir
Figure 6: Linearized Elovich plots Figure 8: Linear plot of the model of Freundlich
It can be noted that ,the pseudo-second order kinetics give The high values of correlation coefficients and the
the highest value of correlation coefficients as compared to negligible deviation between the various models make it
those given by the pseudo-first order, Elovich and difficult to be categorical about which kinetic model fits best.
intraparticle diffusion models. Secondly, all the kinetic In the table 3, the only clear conclusion is that, both
models have high correlation coefficients (R2 > 0.900). physical and chemical adsorptions equally participate in the
overall process of phenol adsorption onto these three
Table 4: Parameters of kinetic models for phenol activated carbons. The correlation coefficients close to the
adsorption on CAH1, CAH2 and CAMH unit in all cases (pseudo second order). These indicate that
the adsorption of phenol from aqueous solution on these three
Adsorbents CAH1 CAH2 CAMH samples obey the pseudo-second order kinetic model. The
K1 (1/min) 0.061 0.081 0.895 applicability of the pseudo-second order model shows that the
Pseudo first Qe (mg/g) 2.447 rate limiting step is chemisorption involving forces caused by
3.728 3.096
order sharing or exchange of electrons between sorbent and sorbate.
R 0.975 0.948 0.954
In the intraparticle diffusion model plots for the adsorption of
K2(g/min.mg) 0.029 0.046 0.048 phenol onto CAH1, CAH2 and CAMH, the straight line do
Pseudo Qe (mg/g) 9.091 9.174 9.901 not pass through the origin indicating that the intraparticle
second
order h 2.398 4.000 4.739 diffusion is not the only process that can control kinetics of
R 0.998 0.999 0.999 adsorption [27], [28]
1.106 1.146 1.316
Elovich Adsorption Isotherms
156.31 412.39 3851.29
The Langmuir, Freundlich, Elovich and Temkin models
R 0.931 0.963 0.982
have been used in this study. The adsorption isotherms relate
Kid(1/min) 0.476 0.374 0.327 the amount of solute adsorbed at equilibrium Qe (mg/g) to the
Intraparticle Xi 5.136 6.192 7.199 phenol concentration at equilibrium, Ce (mg/L) and the plots
diffusion
R 0.937 0.866 0.939 are given in figures 7 to 10. The parameters of the adsorption
isotherm are shown in table 5.
The correlation coefficients of adsorption are quite high for
all the models. The coefficient of adsorption of Langmuir
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International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869, Volume-2, Issue-10, October 2014
aqueous solutions
Adsorbents CAH1 CAH2 CAMH
KL 0.028 0.056 0.924
Langmuir Qe (mg/.g) 19.23 16.39 17.54
R 0.986 0.967 0.978
RL 0.0197 0.01165 0.0007
KF 1.200 2.296 3.428
Freundlich 1/n 0.580 0.436 0.391
R 0.981 0.951 0.965
KE 0.056 0.021 0.399
Elovich Qe (mg/g) 11.236 6.944 6.993
R 0.936 0.913 0.897
Q 11.016
10.275 10.783
Temkin (KJ/mol)
K 0.220 0.485 0.856
R 0.995 0.968 0.956
ACKNOWLEDGMENT
The authors acknowledge the financial support from the
Fig10: Linear plot of Temkin International Foundation for Science (IFS) and Third World
Academy of Science (TWAS). The authors thank also Prof.
is higher for CAH2 and CAMH than the others. This shows Ngoun Jean (University of Dschang) and Prof. Pettinari
that the model of Langmuir describes better the phenomena of (University of Camerino) for their help to CHNS analysis.
adsorption on the surface of these two absorbents. However
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