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Journal of Colloid and Interface Science 286 (2005) 90100

www.elsevier.com/locate/jcis

Equilibrium, kinetics, mechanism, and process design for the sorption


of methylene blue onto rice husk
V. Vadivelan, K. Vasanth Kumar
Department of Chemical Engineering, A.C. Tech, Anna University, Chennai, TN 600 025, India
Received 15 October 2004; accepted 5 January 2005
Available online 16 February 2005

Abstract
Batch experiments were carried out for the sorption of methylene blue onto rice husk particles. The operating variables studied were initial
solution pH, initial dye concentration, adsorbent concentration, and contact time. Equilibrium data were fitted to the Freundlich and Langmuir
isotherm equations and the equilibrium data were found to be well represented by the Langmuir isotherm equation. The monolayer sorption
capacity of rice husks for methylene blue sorption was found to be 40.5833 mg/g at room temperature (32 C). The sorption was analyzed
using pseudo-first-order and pseudo-second-order kinetic models and the sorption kinetics was found to follow a pseudo-second-order kinetic
model. Also the applicability of pseudo second order in modeling the kinetic data was also discussed. The sorption process was found to be
controlled by both surface and pore diffusion with surface diffusion at the earlier stages followed by pore diffusion at the later stages. The
average external mass transfer coefficient and intraparticle diffusion coefficient was found to be 0.01133 min1 and 0.695358 mg/g min0.5 .
Analysis of sorption data using a Boyd plot confirms that external mass transfer is the rate limiting step in the sorption process. The effective
diffusion coefficient, Di was calculated using the Boyd constant and was found to be 5.05 1004 cm2 /s for an initial dye concentration of
50 mg/L. A single-stage batch-adsorber design of the adsorption of methylene blue onto rice husk has been studied based on the Langmuir
isotherm equation.
2005 Elsevier Inc. All rights reserved.
Keywords: Sorption; Rice husk; Methylene blue; Kinetics; Equilibrium; Mechanism; Process design

1. Introduction
Color is a visible pollutant and the presence of even a
very minute amount of coloring substance makes it undesirable due to its appearance. The removal of color from
dye-bearing effluents is a major problem due to the difficulty in treating such wastewaters by conventional treatment
methods. The most commonly used methods for color removal are biological oxidation and chemical precipitation.
However, these processes are effective and economic only in
the case where the solute concentrations are relatively high.
Most industries use dyes and pigments to color their products [1]. Most dye-containing effluents from various industrial branches are discharged into the river streams mainly
* Corresponding author.

E-mail address: vasanth_vit@yahoo.com (K.V. Kumar).


0021-9797/$ see front matter 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.01.007

from dye manufacturing and textile finishing industries. Currently the sorption technique is proved to be an effective
and attractive process for the treatment of these dye-bearing
wastewaters [25]. Also this method will become inexpensive, if the sorbent material used is of cheaper cost and does
not require any expensive additional pretreatment step. In the
present study rice husks, an agro-based waste material have
been used as adsorbent for the removal of methylene blue
from its aqueous solution. Methylene blue is selected as a
model compound in order to evaluate the capacity of rice
husk for the removal of dye (methylene blue) from its aqueous solutions. Methylene blue has wider applications, which
include coloring paper, temporary hair colorant, dyeing cottons, wools, and coating for paper stock. Though methylene
blue is not strongly hazardous, it can cause some harmful effects. Acute exposure to methylene blue will cause increased
heart rate, vomiting, shock, Heinz body formation, cyanosis,

V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

91

jaundice, quadriplegia, and tissue necrosis in humans. Previously several researchers had proved several low-cost materials such as pear millet husk carbon [6], brown coal fly
ash [7], rice husk [8], hair [8], cotton waste [8], bark [8],
perlite [9], raw kaolin [10], pure kaolin [10], calcined raw
kaoline [10], calcined pure kaoline [10], NaOH-treated raw
kaolin [10], coir pith [11], guava seed-activated carbon [12],
iron humate [7], neem sawdust [13], and clay [14] for the
removal of methylene blue from its aqueous solutions. Previously McKay et al. [8] reported on the removal of methylene
blue by rice husks. However, the kinetic aspects involved
in the sorption process were not discussed. In the present
study rice husks have been used as an adsorbent for the removal of methylene blue from its aqueous solutions. The dye
methylene blue is selected as a model compound in order
to evaluate the capability of rice husks to remove dye from
wastewaters. Also the sorption of methylene blue at solid
liquid interfaces has been studied extensively under equilibrium conditions. Further the kinetics and the mechanistic
steps involved in the sorption process were evaluated at different initial methylene blue concentrations. A single-stage
batch sorber has been designed for the removal of methylene
by rice husks based on the equilibrium data obtained.

2.2.2. Effect of adsorbent concentration


The effect of rice husk mass on the amount of color adsorbed was obtained by contacting 30 mL of dye solution of
initial dye concentration 100 mg/L with different weighed
amounts (0.12, 0.08, 0.065, 0.05, 0.04, 0.03, and 0.02 g)
of rice husk using water-bath shakers at room temperature
(32 C) for 48 h, which is more than sufficient time to reach
equilibrium at a constant stirring speed of 95 strokes/min.
After equilibration, the samples were then centrifuged and
the concentration in the supernatant dye solution was analyzed as before. All the experiments were carried out at an
optimum pH of 8.

2. Experimental

2.2.4. Sorption equilibrium


Equilibrium experiments were carried out by contacting
0.06 g of rice husk particles with 50 mL of dye solution of
different initial dye amounts, 125, 100, 70, 50, 30, 10 mg/L.
The contact was made in 150-mL conical flasks using waterbath shakers at a constant agitation speed of 95 strokes/min.
The agitation was made for 48 h, which is more than sufficient time to reach equilibrium.

2.1. Materials
The rice husk used in the present investigation was obtained from local rice mills. The collected materials were
then washed with distilled water for several times to remove
all the dirt particles. The washing process was continued till
the wash water contains no color. The washed materials were
then dried in a hot air oven at 60 C for 24 h. The dried materials were then ground using a domestic mixer. The ground
materials were then sieved to constant particle sizes of +60
to 85 mesh. The materials were then stored in plastic bottles for use.

2.2.3. Sorption kinetics


Sorption kinetics experiments were carried out using
magnetic stirrers of 1-L capacity. Kinetic experiments were
carried out by agitating 1 L of dye solution of known initial dye concentration 100 mg/L with 4 g of rice husks in
1.5-L beakers at room temperature (32 C) at an optimum
pH of 8 and at a constant agitation speed of 800 rpm. Samples (2.5 mL) were pipetted out using a 10 mL-syringe at
different time intervals. The collected samples were then
centrifuged and the concentration in the supernatant solution
was analyzed using a UV spectrophotometer.

3. Results and discussion


3.1. Effect of pH

2.2. Sorption experiments

Fig. 1 shows the effect of pH on amount of dye adsorbed


qe (mg/g). Where qe was obtained from the mass balance
equation given by

2.2.1. Effect of pH
The effect of pH on the amount of color removal was analyzed over the pH range from 3 to 8. The pH was adjusted
using 0.1 N NaOH and 0.1 N HCl solutions. In this study
50 mL of dye solution of 100 mg/L was agitated with 0.03 g
of rice husk using water-bath shakers at room temperature
(32 C). Agitation was made for 48 h which is more than
sufficient to reach equilibrium at a constant agitation speed
of 95 strokes/min. The samples were then centrifuged and
the left out concentration in the supernatant solution was analyzed using a UV spectrophotometer (Deep Vision 301 E)
by monitoring the absorbance changes at a wavelength of
maximum absorbance (665 nm).

(C0 Ce )V
(1)
,
M
where C0 (mg/L) and Ce (mg/L) are the concentration in
the solution at time t = 0 and at equilibrium time t, V is
the volume of solution treated (L), and M is the amount of
biomass added (g). From Fig. 1, it was observed that the
solution pH affects the amount of dye adsorbed. The dye
uptake was found to increase with increasing pH and it increases from 43.333 to 80.791 mg/g for an increase in pH
from 3 to 8. Several reasons may be attributed to dye sorption
behavior of the sorbent relative to solution pH. The surface
of rice husks may contain a large number of active sites and
the solute (dye ions) uptake can be related to the active sites
qe =

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V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

Fig. 1. Effect of initial pH (C0 , 100 mg/L; V , 50 mL; M, 0.03 g).

and also to the chemistry of the solute in the solution. At


lower pH, the surface charge may get positively charged,
thus making H+ ions compete effectively with dye cations
causing a decrease in the amount of dye adsorbed (mg/g).
At higher pH the surface of rice husk particles may get negatively charged, which enhances the positively charged dye
cations through electrostatic forces of attraction.
3.2. Effect of adsorbent concentration
Fig. 2 shows the plot between amount of dye adsorbed qe
against adsorbent concentration (g). From the figure it was
observed that, the amount of dye adsorbed is varied with
varying sorbent mass and it decreased with increase in adsorbent mass. The amount of dye adsorbed decreases from
427.5 to 221.75 mg/g for an increase in adsorbent mass from
0.02 to 0.12 g, whereas the percentage color removal increased from 28.5 to 88.7% with an increase in adsorbent
mass from 0.02 to 0.12 g. At higher rice husk to solute concentration ratios, there is a very fast superficial sorption onto
the adsorbent surface that produces a lower solute concentration in the solution than when the biomass to solute concentration ratio is lower. This is because a fixed mass of rice
husk can only adsorb a certain amount of dye. Therefore,
the more the adsorbent dosage, the larger the volume of effluent that a fixed mass of rice husk can purify. The decrease
in amount of dye adsorbed qe (mg/g) with increasing adsorbent mass is due to the split in the flux or the concentration
gradient between solute concentration in the solution and the
solute concentration in the surface of the adsorbent. Thus
with increasing adsorbent mass, the amount of dye adsorbed
onto unit weight of adsorbent gets reduced, thus causing a
decrease in qe value with increasing adsorbent mass concentration.

Fig. 2. Effect of adsorbent mass (C0 , 100 mg/L; V , 50 mL; pH, 8; temperature, 32 C).

3.3. Sorption kinetics


The prediction of batch sorption kinetics is necessary for
the design of industrial sorption columns. The nature of the
sorption process will depend on physical or chemical characteristics of the adsorbent system and also on the system
conditions. Previously several researchers used different kinetic models, such as Lagergren pseudo first order, pseudo
second order, Elovich kinetic equation, and parabolic diffusion model, in order to predict the mechanism involved in the
sorption process. From these models the sorption kinetics
was usually described by the Lagergren pseudo-first-order
model [6,15,16]. Currently the pseudo-second-order model
has been widely used for sorption systems due to its good
representation of the experimental data for most of the adsorbent adsorbate systems. In the present study, the applicability of the pseudo-first-order and pseudo-second-order model
has been tested for the sorption of methylene blue onto rice
husk particles. The best-fit model was selected based on the
linear regression correlation coefficient, r 2 values.
Fig. 3 shows a plot of the amount of dye adsorbed (mg/g)
versus contact time for different initial methylene blue concentrations of 100, 70, and 50 mg/L. From the figure it was
observed that the amount of dye uptake, qe (mg/g), is increased with contact time at all initial dye concentrations.
Further the amount of dye adsorbed is increased with increase in initial dye concentration. For the first 10 min, the
sorption rate was found to increase from 0.6378 to 2.82121
mg/g min for an increase in initial dye concentration from
50 to 100 mg/L. A similar observation was observed at
all initial dye concentrations over the entire concentration
ranges studied. From the figure it was also observed that dye
uptake is rapid for the first 40 min and thereafter it proceeds
at a slower rate and finally attains saturation. These observations show that the initial dye concentration has no effect

V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

Fig. 3. Adsorption kinetics for methylene blue onto rice husk (C0 ,
100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800 rev min1 ).

on equilibrium time. Also up to 6070% of the total amount


of dye uptake was found to occur in the first rapid phase
(40 min) and thereafter the sorption rate was found to decrease. The sorption rate for the first 40 min was found to be
0.1083, 0.2194, and 0.2986 mg/g min for an initial dye concentration of 50, 70, and 100 mg/L. After 40 min the sorption rate decreased to 0.029, 0.0302, and 0.0185 mg/g min
for an initial dye concentration of 50, 70, and 100 mg/L.
The higher sorption rate at the initial period (first 40 min)
may be due to an increased number of vacant sites available
at the initial stage, as a result there exist increased concentration gradients between adsorbate in solution and adsorbate in
the adsorbent surface. This increase in concentration gradient tends to increase in dye sorption rate at the initial stages.
As time proceeds this concentration is reduced due to the accumulation of dye particles in the vacant sites, leading to a
decrease in sorption rate at later stages from 40 to 150 min.
The transient behavior of the dye sorption process was
analyzed using the pseudo first order and pseudo second order are explained as follows:
3.3.1. Lagergren pseudo-first-order kinetics
The pseudo-first-order kinetic model has been widely
used to predict the dye sorption kinetics. The dye sorption
kinetics following the pseudo-first-order model is given by
[2,17]
dq
= K1 (qe q),
(2)
dt
where q and qe represent the amount of dye adsorbed (mg/g)
at any time t and at equilibrium time, respectively, and K1
represents the sorption rate constant (min1 ). Integrating

93

Fig. 4. Lagergren pseudo-first-order kinetics for methylene blue onto rice


husk (C0 , 100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800
rev min1 ).
Table 1
Pseudo-first-order rate constant for the sorption of methylene blue onto rice
husk
C0 (mg/L)

K1 (min1 )

r12

50
70
100

0.0249
0.02772
0.04515

0.996096
0.989395
0.992677

Eq. (2) with respect to boundary conditions q = 0 at t = 0


and q = q at t = t, then Eq. (2) becomes
log(qe /qe q) =

K1 t
.
2.303

(3)

Thus the rate constant K1 (min1 ) can be calculated from


the plot of log(qe /qe q) versus time t. Fig. 4 shows the plot
between log(qe /qe q) versus time t. The rate constant K1
was calculated from the slope of Fig. 4. The calculated K1
values and the corresponding linear regression correlation
coefficient r12 values are shown in Table 1. From Table 1,
it was observed that the rate constant K1 is increased with
increase in initial dye concentration. The relation between
initial dye concentration C0 and rate constant K1 was found
to fit the relation with a correlation coefficient of 1 as follows:
K1 = 1 105 (C0 )2 0.0013(C0 ) + 0.0631,

r 2 = 1.

(4)
Further from Table 1, it was observed that correlation coefficients were higher for all ranges of initial dye concentrations studied (50 to 100 mg/L). This shows the applicability

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V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

of the pseudo-first-order model in predicting the kinetics of


the methylene blue adsorption onto rice husk particles.
3.3.2. Ho pseudo-second-order kinetics
The kinetic data were further analyzed using Hos pseudosecond-order kinetics, which is represented by [18]
dq
(5)
= K2 (qe q)2 ,
dt
where K2 is the pseudo-second-order rate constant (g/
mg min), qe and q represent the amount of dye adsorbed
(mg/g) at equilibrium and at any time t. Separating the variables in Eq. (5) gives
dq
= K2 dt.
(qe q)2

(6)

Integrating Eq. (6) for the boundary conditions t = 0 to t = t


and q = 0 and q = qe gives
1
t
1
=
+ t.
2
q
qe
K2 qe

(7)

A plot between t/q versus t gives the value of the constants


K2 (g/mg h) and also qe (mg/g) can be calculated.
The constant K2 is used to calculate the initial sorption
rate h, at t 0, as follows:
h = K2 qe2 .

(8)

Thus the rate constant K2 , initial sorption rate h, and predicted qe can be calculated from the plot of t/q versus time
t using Eq. (7).
Fig. 5 shows the plot between t/q versus time t. The initial sorption rate h, pseudo-second-order-rate constant K2 ,
amount of dye adsorbed at equilibrium qe , and the corresponding linear regression correlation coefficient r22 values
are given in Table 2. From Table 2 it was observed that the
r22 values were found to be higher than that of r12 at all initial dye concentrations. Also the r22 values were found to
be in the range of 0.995985 to 0.999136. The higher values r22 values confirm that the sorption process follows a
pseudo-second-order mechanism. Also this suggests the assumption behind the pseudo-second-order model that the
dye uptake process is due to chemisorption [18]. Chemical
sorption can occur by the polar functional groups of lignin,
which include alcohols, aldehydes, ketones, acids, phenolic hydroxides, and ethers as chemical bonding agents [18].
From Table 2, it was also observed that the initial sorption rate h, pseudo-second-order-rate constant K2 , and the
equilibrium sorption capacity are increased with increase in
initial dye concentration. A similar observation was previously reported by Ho [18] for copper ions onto tree fern
adsorbent. The corresponding linear plots of K2 , h, and qe
can be expressed as a function of C0 for methylene blue
as
K2 = 0.0002C0 0.00533,
h = 0.011262C0 0.30005,

Fig. 5. Ho pseudo-second-order kinetics for methylene blue onto rice husk


(C0 , 100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800 rev min1 ).

r 2 = 0.922848,
r = 0.922848,
2

(9)
(10)

Table 2
Pseudo-second-order rate constant for the sorption of methylene blue onto
rice husk
C0 (mg/L)

K2 (g/mg min)

h (mg/g min)

qe, predicted
(mg)

r22

50
70
100

0.003224
0.011075
0.0137

0.181647
0.623958
0.771878

11.29793
14.60515
19.28963

0.996964
0.999136
0.995985

qe, predicted = 0.0159543C0 + 3.364409,


r 2 = 0.922848.

(11)

3.3.3. Comparison of kinetic models and kinetic modeling


The calculated correlation coefficient values for firstorder (0.9893950.996096) and second-order (0.995985
0.999136) kinetics were found to be greater than 0.9, which
shows the applicability of both these kinetic models. Thus in
the present both the pseudo-first-order and pseudo-secondorder kinetic expressions were tested for its consistency in
predicting the amount of dye adsorbed for the entire sorption time. The q values were predicted by applying the calculated kinetic constants in their corresponding kinetic expressions. Thus applying the pseudo-first-order rate constant
in Eq. (3), the pseudo-first-order kinetic rate expression for
methylene blue onto rice husk was calculated and shown in
Table 3.
Similarly the pseudo-second-order kinetic expression can
be obtained by substituting the K2 , predicted qe value in a

V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

95

Table 3
Predicted pseudo-first-order equation for the sorption of methylene blue
onto rice husk
C0 (mg/L)

Predicted Lagergren I
order equation

50

q = 7.7345 7.7345
0.0249t

70

q = 12.7345 12.7345
0.02772t

100

q = 16.01482 16.01482
0.04515t

exp

exp

exp

Table 4
Predicted second-order equation for the sorption of methylene blue onto
rice husk
C0 (mg/L)

Predicted Lagergren I
order equation

70

t
q = 0.181647+t/11.29793
t
q = 0.623958+t/14.60515

100

t
q = 0.771878+t/19.28963

50

Fig. 7. Predicted q values for different initial dye concentrations (conditions: pH, 8; rpm, 800 rev min1 ; temperature, 32 C; V /X, 1 L/4 g).

suggests the Ho pseudo-second-order kinetic model can be


applied to predict the amount of dye uptake at different contact time intervals and at equilibrium. This is in agreement
with higher r22 values than r12 for all the initial dye concentrations studied. The general Ho pseudo-second-order expression that can be used to predict the value of q for any of
the concentration ranges (50100 mg/L) under the present
study is given by
t
.
q=
2
0.0003C0 + 0.0634C0 2.1271 + 14.502C01.2144 t
(13)
Equation (13) can be used to predict the q value at any
time for any of the initial dye concentration required. The
predicted q values for different initial dye concentrations using Eq. (13) for a fixed V /X ratio of 1 L/4 g is shown in
Fig. 7.
Fig. 6. Comparison of kinetic models in predicting q for methylene blue
onto rice husk (C0 , 100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800
rev min1 ).

rearranged form of Eq. (7) which is given by


q=

t
.
(K2 qe2 ) + (1/qe )t

(12)

The predicted pseudo-second-order kinetic expression at different initial dye concentrations are given in Table 4.
The q values predicted from Lagergren pseudo-first-order
kinetics and Ho pseudo-second-order kinetics are shown in
Fig. 6. From Fig. 6, it was observed that for the entire sorption period, pseudo-second-order expression better predicts
the sorption kinetics than the pseudo-first-order model. This

3.4. Sorption equilibrium


The analysis and design of the sorption process requires
the relevant adsorption equilibria, which is the most important piece of information in understanding an adsorption
process [19]. Sorption equilibria provide fundamental physiochemical data for evaluating the applicability of the sorption process as a unit operation. The two most commonly
used equilibrium relations are Freundlich and Langmuir
isotherm equations. In the present investigation the equilibrium data were analyzed using the Freundlich and Langmuir
isotherm expression given by Eq. (14) and Eq. (15), respectively,
Freundlich,

1/n

qe = Kf Ce ,

(14)

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V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

q0 KL Ce
,
(15)
1 + KL Ce
where Kf and n are Freundlich constants related to sorption
capacity and sorption intensity of adsorbents. The value of n
falling in the range of 110 indicates favorable sorption. The
linearized form of Freundlich and Langmuir can be written
as follows:
Langmuir,

qe =

log qe = log Kf + 1/n(log Ce ),

(16)

Ce /qe = 1/KL q0 + Ce /q0 .

(17)

Thus the Freundlich constant Kf and n can be calculated from the intercept and slope of plot between log qe and
log Ce . Similarly the Langmuir constants q0 and KL were
calculated from the slope of plot between Ce /qe versus Ce .
The predicted Freundlich and Langmuir isotherm equation
for methylene blue onto rice husk particles useful for design
calculations are given by Eqs. (18) and (19), respectively:
qe = 8.628196Ce0.382809 ,
(18)
5.590999Ce
.
qe =
(19)
1 + 0.13776Ce
Fig. 7 shows the Freundlich and Langmuir curve for methylene blue onto rice husk at a constant solution temperature of 32 C along with the experimental data. The Freundlich and Langmuir curves in Fig. 8 were generated using

Eqs. (18) and (19). From Fig. 8 it was observed that the
equilibrium data were very well represented by the Langmuir isotherm equation when compared to the Freundlich
equation. The sorption equilibrium data fit Freundlich and
Langmuir equations with a correlation coefficient value of
0.968246 and 0.984986, respectively. The best fit of equilibrium data in the Langmuir isotherm expression confirms the
monolayer coverage of methylene blue onto rice husk particles. The calculated Freundlich and Langmuir isotherm constants, predicted Freundlich and Langmuir equations, and
their corresponding linear regression correlation coefficient
values at 32 C are given in Table 5. From Table 5, it was
observed that the maximum sorption capacity of rice husk
particles for methylene blue was found to be 40.5833 mg/g.
The qm values show that the sorption capacity of rice husk
particles was highly comparable to the sorption capacities of
some other low-cost adsorbent materials for methylene blue.
The essential characteristics of the Langmuir isotherm
can be expressed in terms of dimensionless constant separation factor or equilibrium parameter, RL , given by [20]
RL = 1/(1 + KL C0 ).

(20)

The parameter RL indicated the shape of isotherm as follows:


Value of RL

Type of isotherm

RL > 1
RL = 1
0 < RL < 1
RL = 0

Unfavorable
Linear
Favorable
Irreversible

The calculated RL values at different initial methylene blue


concentration is shown in Fig. 9. From Fig. 9 it was observed
that sorption was found to be more favorable at higher concentrations. Also the value of RL in the range of 0 to 1 at all
initial dye concentration confirms the favorable uptake of the
methylene blue process. Also higher RL values at lower dye
concentrations show that the adsorption is more favorable at
lower dye concentrations.
3.5. Sorption mechanisms

Fig. 8. Equilibrium curve for the sorption of methylene blue onto rice husk
at 32 C (V , 50 mL; M, 0.06 g; pH, 8; agitation speed, 95 stroke min1 ).

From a mechanistic viewpoint to interpret the experimental data, prediction of the rate-limiting step is an important
factor to be considered in the sorption process [21]. Though
kinetic and equilibrium isotherm studies help to identify the
sorption process, predicting the mechanisms is required for
design purposes. For a solid liquid sorption process, the
solute transfer is usually characterized by either external

Table 5
Equilibrium constants for methylene blue onto rice husk at 32 C
Temperature
( C)

Langmuir isotherm parameters


q0 (mg/g)

32

40.5883

Freundlich isotherm parameters

KL

r2

Kf (mg/g)(L/g)

1/n

r2

0.137766

0.984986

8.628196

0.36289

0.968246

V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

Fig. 9. Separation factor for methylene blue onto rice husk at 32 C.

mass transfer (boundary layer diffusion) or intraparticle diffusion or both. The sorption dynamics can be described by
the following three consecutive steps which are as follows:
Transport of the solute from bulk solution through liquid
film to the adsorbent exterior surface;
Solute diffusion into the pore of adsorbent except for a
small quantity of sorption on the external surface; parallel to this is the intraparticle transport mechanism of the
surface diffusion;
Sorption of solute on the interior surfaces of the pores
and capillary spaces of the adsorbent.
The last step is considered to be an equilibrium reaction.
Of the three steps, the third step is assumed to be rapid and
considered to be negligible. The overall rate of sorption will
be controlled by the slowest step, which would be either
film diffusion or pore diffusion. However, the controlling
step might be distributed between intraparticle and external
transport mechanisms. Whatever the case, external diffusion
will be involved in the sorption process. The sorption of
methylene blue onto rice husk particles may be controlled
due to film diffusion at earlier stages and as the adsorbent
particles are loaded with dye ions, the sorption process may
be controlled due to intraparticle diffusion. But for design
purposes, it is necessary to calculate the slowest step involved in the sorption process. For the sorption process, the
external mass transfer controls the sorption process for the
systems that have poor mixing, dilute concentration of adsorbate, small particle sizes of adsorbent, and higher affinity
of adsorbate for adsorbent. Whereas the intraparticle diffusion will control the sorption process for a system with good

97

mixing, large particle sizes of adsorbent, high concentration


of adsorbate, and low affinity of adsorbate for adsorbent.
In general, external mass transfer is characterized by the
initial solute uptake [4,5] and can be calculated from the
slope of plot of C/C0 versus time. The slope of these plots
can be calculated either by assuming polynomial relation between C/C0 and time or it can be calculated based on the
assumption that the relationship was linear for the first initial rapid phase (in the present study first 40 min). The later
technique was used by Fernadez et al. [22] for lauryl benzyl
sulfonate onto algal residue. In the present study the second technique was used by assuming that the external mass
transfer occurs in the first 40 min. Thus the initial sorption
rates Ks (min1 ) were quantified as (C40 min /C0 )/40. The
calculated Ks value for the methylene blue onto rice husk
particles was given by 0.00865, 0.01304, and 0.0123 min1
for an initial dye concentration of 50, 70, and 100 mg/L.
The most commonly used technique for identifying the
mechanism involved in the sorption process is by fitting the
experimental data in an intraparticle diffusion plot. Previous studies by various researchers showed that the plot of q
versus t 0.5 represents multilinearity, which characterizes the
two or more steps involved in the sorption process [17,23].
According to Weber and Morris, an intraparticle diffusion
coefficient Ki is defined by the equation:
Ki = q/t 0.5 .

(21)
(mg/g min0.5 )

value can be obtained from the


Thus the Ki
slope of the plot of q (mg/g) versus t 0.5 (min0.5 ). Fig. 10
shows the plot of q versus t 0.5 for methylene blue onto rice
husk particles. From Fig. 10, it was noted that the sorption
process tends to be followed by two phases. It was found that
the linear portion ended with a smooth curve followed by a
linear portion. A similar type of pattern was reported previously by Sankar et al. [24] for acid and direct dye onto
rice bran-activated carbon and also by Sivaraj et al. [17]
for acid violet onto orange peel. The two phases in the intraparticle diffusion plot suggest that the sorption process
proceeds by surface sorption and intraparticle diffusion. The
initial curved portion of the plot indicates a boundary layer
effect while the second linear portion is due to intraparticle
or pore diffusion. The slope of the second linear portion of
the plot has been defined as the intraparticle diffusion parameter Ki (mg/g min0.5 ). On the other hand, the intercept of
the plot reflects the boundary layer effect. The larger the intercept, the greater the contribution of the surface sorption
in the rate-limiting step. The calculated intraparticle diffusion coefficient Ki value was given by 0.53846, 0.714285,
and 0.83333 mg/g min0.5 for an initial dye concentration of
50, 70, and 100 mg/L.
As the double nature of intraparticle diffusion plot confirms the presence of both film and pore diffusion, in order
to predict the actual slow step involved, the kinetic data were
further analyzed using the Boyd kinetic expression. This kinetic expression predicts the actual slowest step involved in
the sorption process for different sorbent sorbate systems.

98

V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

Fig. 11. Plot of Bt versus t (Boyd plot).

Fig. 10. Intraparticle diffusion plot for methylene blue onto rice husk (C0 ,
100 mg/L; V , 1 L; M, 4 g; pH, 8; agitation speed, 800 rev min1 ).

The Boyd kinetic expression is given by [25]


F = 1 (6/ 2 ) exp(Bt)

(22)
3.6. Design of batch sorption from isotherm data

and
F = q/q0 ,

(23)

where q0 is the amount of methylene blue adsorbed at infinite time (mg/g) and q represents the amount of dye adsorbed at any time t (min), F represents the fraction of solute
adsorbed at any time t, and Bt is a mathematical function
of F .
Substituting Eq. (23) in (22), Eq. (22) simplifies to
1 F = (6/ 2 ) exp(Bt)

(24)

or
Bt = 0.4977 ln(1 F ).

(25)

The Bt values at different contact times can be calculated using Eq. (25). The calculated Bt values were plotted against
time t as shown in Fig. 11. Fig. 11 is used to identify whether
external transport or intraparticle transport control the rate of
sorption [1,21,25]. From Fig. 11, it was observed that the
plots were linear but do not pass through the origin confirming that, for the studied initial dye concentration, external mass transport mainly governs the sorption process
[1,21,25]. The calculated B values were used to calculate
the effective diffusion coefficient, Di (cm2 /s) using the relation [26]
B = 2 Di /r 2 ,

where r represents the radius of the particle calculated by


sieve analysis and by assuming spherical particles. The Di
values were found to be 3.10601 1005 , 2.41449 1005 ,
and 5.48534 1005 cm2 /s for an initial methylene blue
concentration of 50, 70, and 100 mg/L.

(26)

Generally the sorption process proceeds through varied


mechanisms such as external mass transfer of solute onto
sorbent followed by intraparticle diffusion. Unless extensive experimental data are available concerning the specific
sorption application, determining the rate-controlling step is
impossible. Therefore, empirical design procedures based
on sorption equilibrium conditions are the most common
method for predicting the adsorber size and performance.
Sorption equilibrium is a dynamic concept achieved when
the rate at which molecules adsorb onto a surface is equal
to the rate at which they desorb. The physical chemistry involved may be complex and no single theory of sorption
has been put forward to explain all the systems. Fortunately,
engineering requires only the data under equilibrium conditions. Previously sorption isotherm relations were used to
predict the design of single-stage batch-sorption systems [2,
2729]. A schematic diagram is shown in Fig. 12. The design objective is to reduce the dye solution of volume V
(L) from an initial concentration of C0 to C1 (mg/L). The
amount of adsorbent is M and the solute loading changes
from q0 (mg/g) to q1 (mg/g). At time t = 0, q0 = 0 and
as time proceeds the mass balance equates the dye removed
from the liquid to that picked up by the solid. The mass
balance equation for the sorption system in Fig. 12 can be

V. Vadivelan, K.V. Kumar / Journal of Colloid and Interface Science 286 (2005) 90100

99

Fig. 12. Single-stage batch-adsorber design.

written as
V (C0 C1 ) = M(q0 q1 ) = Mq1 .

(27)
Fig. 13. Adsorbent mass (M) against volume of solution treated (L).

Under equilibrium conditions,


C1 Ce

and q1 qe .

(28)

Since the sorption isotherm studies confirm that the equilibrium data for methylene blue onto rice husk particle fitted
well in a Langmuir isotherm, a Langmuir isotherm equation
can be used for q1 in equation batch adsorber design.
Equation (23) can be rearranged as
(C0 Ce ) C0 Ce C0 Ce
M
=
=
= qK C .
0 L e
V
q1
qe

(29)

1+KL Ce

Fig. 13 shows the plot between the predicted amount of rice


husk particles required to remove dye solutions of initial
concentrations 100 mg/L for 90, 80, 70, and 60% color removal at different solution volumes (1, 2, 3, 4, 5, 6, 7 L). For
a single-stage batch-sorption system, the design procedure
is outlined. For example, the amount of rice husk required
for the 90% removal of methylene blue solution of concentration 100 mg/L was 3.827393, 7.654786, 11.48218, and
15.30957 g for dye solution volumes of 1, 2, 3, and 4 L, respectively.

4. Conclusion
1. The present study shows that the rice husk, an agrobased waste biomaterial can be used as an adsorbent for
the removal of methylene blue from its aqueous solutions.
2. The amount of dye sorbed was found to vary with initial
solution pH, adsorbent dose, and contact time.
3. The amount of dye uptake (mg/g) was found to increase
with increase in solution concentration and contact time
and found to decrease with increase in adsorbent dosage.

4. The sorption data were found to follow pseudo-secondorder kinetics.


5. Equilibrium data fitted very well in a Langmuir isotherm
equation, confirming the monolayer sorption capacity of
methylene blue onto rice husk particles with a monolayer sorption capacity of 40.5833 mg/g.
6. The dye uptake process was found to be controlled by
external mass transfer at earlier stages and by intraparticle diffusion at later stages.
7. A Boyd plot confirms the external mass transfer as the
slowest step involved in the sorption process.

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