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EQUILIBRIUM, KINETICS, AND

BREAKTHROUGH STUDIES FOR
ADSORPTION OF Cr(VI) ON CHITOSAN
a

S. Bhuvaneshwari & V. Sivasubramanian

a
Department of Chemical Engineering , National Institute of
Technology , Calicut , Kerala , India
Accepted author version posted online: 28 Oct 2013.Published
online: 25 Feb 2014.

To cite this article: S. Bhuvaneshwari & V. Sivasubramanian (2014) EQUILIBRIUM, KINETICS,

AND BREAKTHROUGH STUDIES FOR ADSORPTION OF Cr(VI) ON CHITOSAN, Chemical Engineering
Communications, 201:6, 834-854, DOI: 10.1080/00986445.2013.793674
To link to this article: http://dx.doi.org/10.1080/00986445.2013.793674

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Chem. Eng. Comm., 201:834854, 2014

Copyright # Taylor & F rancis G roup, LLC
ISSN: 0098-6445 print=1563-5201 online
DOI: 10.1080/ 00986445.2013.793674

Equilibrium, Kinetics, and Breakthrough Studies for

Adsorption of Cr(VI) on Chitosan
S. BHUVANESHWARI AND V. SIVASUBRAMANIAN

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Department of Chemical Engineering, National Institute of Technology,

Calicut, K erala, India
Wastewater containing low levels of pollutants can be effectively treated by the
adsorption technique. In the present work, an adsorption study was carried out using
chitosan as adsorbent in a fixed-bed column for the removal of Cr( VI) from wastewater solutions. The column performance of Cr( VI) adsorption onto chitosan was
studied at different bed heights ( 39 cm) , flow rates ( 50200 mL=min) , initial metal
concentrations ( 210 mg=L) , pH values ( 27) , and temperatures ( 30 60 C) . The
equilibrium data for the batch adsorption of Cr( VI) on chitosan were tested using
the Langmuir, Freundlich, and BET isotherm models. The Langmuir model was
found to be the most suitable, with a maximum adsorption capacity of 35.7 mg=g
and a correlation coefficient ( R 2) 0.952. The experimental data were found to
fit well with the pseudo-second-order kinetic model, with R 2 0.999. The dynamics
of the adsorption process was modeled using the Adams-Bohart, Thomas, and mass
transfer models. The models were used to predict the breakthrough curves of adsorption systems and to determine the characteristic design parameters of the column.
The adsorption data were observed to fit well with all three models. The model parameters were derived using M ATLAB software. In order to compare quantitatively
the applicability of adsorption dynamic models in fitting to experimental data, the
percentage relative deviation ( P) was calculated and found to be less than 5, confirming that the fit is good for all three models.
Keywords Bed depth; Breakthrough data; Flow rate and models

Introduction
Water pollution has become a major threat to society due to rapid industrialization
and severe exploitation of natural resources. Water pollution results in the deterioration of water quality, thereby leading groundwater deposits and aquatic ecosystems to the danger of exhaustion. On a small scale, both inorganic and organic
pollutants safely decompose throughout the water stream; their concentration
decreases continuously and thus they do not harm the aquatic ecosystem. H owever,
on an excessive scale, aquatic communities will be affected by pollutants and suffer
profound harm (Schmitz, 1995).
H eavy metals are chemical elements with a specific gravity at least five times that
of water. Heavy metals become toxic when they are not metabolized by the living
Address correspondence to V. Sivasubramanian, D epartment of Chemical Engineering,
National Institute of Technology, Calicut, K erala 673601, India. E-mail: siva@nitc.ac.in
Color versions of one or more of the figures in the article can be found online at
www.tandfonline.com/ gcec.

834

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Adsorption of Cr( VI) on Chitosan

835

body and accumulate in the soft tissues (Duffus, 2002; Jeon et al., 2001). Some of the
common heavy metals in waste streams are antimony, arsenic, bismuth, cadmium,
cerium, chromium, cobalt, copper, gallium, gold, iron, lead, manganese, mercury,
nickel, platinum, silver, tellurium, thallium, tin, uranium, vanadium, and zinc.
Hexavalent chromium is used for the production of stainless steel, textile dyes,
wood preservation, leather tanning, plastics, inks, and paints (Bielicka et al.,
2005). It is a heavy metal commonly found at low levels in drinking water. It can
occur naturally and can also enter drinking water sources by significant leaks from
industrial plants hazardous waste sites. Cr(VI) is known to be a potent carcinogen
when inhaled. Among the different physicochemical treatments employed for wastewater treatment, the adsorption technique has been found to be very effective to
treat effluents with high loadings of contaminants at dilute concentrations, typically
< 100 mg=L. Commercial adsorbents like activated carbon are highly efficient but are
costly. Use of natural materials like clay, chitosan, zeolite, banana pith, rice husk,
and peat have therefore gained attention, particularly due to their selectivity, nontoxicity, and availability (Varma et al., 2004; Veglio and Beolchini, 1997).
An adsorption process generally involves a:
1. Sorbent or biosorbent, a solid phase (biological material), and
2. Sorbate, a liquid phase (solvent is normally water) containing a dissolved species
(metal ions) to be adsorbed.
Due to the high affinity of the sorbent for the sorbate species, the latter is attracted
and bound to the former by different mechanisms. The process continues until
equilibrium is established between the amount of solid-bound sorbate species and
its portion remaining in the solution. The degree of sorbent affinity for the sorbate
determines its distribution between the solid and liquid phases (Ahalya et al., 2003).
The major advantages of adsorption over conventional treatment methods are low
cost, high efficiency, minimization of chemical and or biological sludge, less nutrient
requirement, regeneration of biosorbent, and the possibility of metal recovery (Alluri
et al., 2007). Among the biopolymers derived from seafood wastes and natural
substances, chitosan has the highest metal-chelating capacity. It contains hydroxyl
(-OH ) and amino (-N H 2) groups, which serve as binding sites for transition of metals
(Futalan et al., 2011; Guibal, 2004).
The design of a continuous packed bed column for adsorption of heavy metals
depends on parameters such as adsorbent size, column bed height, flow rate of metal
solution into the column, initial concentration of metal solution, temperature, and
pressure of the operating system (Zhou et al., 2004). In a fixed-bed adsorption system, the adsorbent located closer to raw water saturates first where maximum
adsorption takes place initially. This adsorption zone moves further as time passes
and then approaches the exit of the bed. When the adsorption zone has moved
through the column, the concentration of the adsorbate at the exit becomes equal
to the feed concentration. A plot of exit concentration as a function of lapsed time
or volume throughput reacted is known as the breakthrough curve. The characteristic shape of the curve depends on inlet flow rates, concentration, and other properties such as column diameter and bed height. The area under the breakthrough curve
gives the total quantity of metal sorbed for a given feed concentration (Ayoob et al.,
2007; Ghorai and Pant, 2005).
The present investigation focuses on the adsorption of Cr(VI) from wastewater
streams using a fixed-bed column packed with chitosan. The design of the column

836

S. Bhuvaneshwari and V. Sivasubramanian

was based on breakthrough curves. The characteristic parameters of the column such
as adsorption rate coefficient and maximum adsorption capacity of an adsorbent
were evaluated using the Adams-Bohart, Thomas, and mass transfer adsorption
models. Experimental and theoretical studies for adsorption of Cr(VI) from aqueous
solutions were carried out. The simulation study for Cr(VI) adsorption onto chitosan
was achieved using linear regression analysis (MATLAB). Initially, adsorption tests
of Cr(VI) from synthetic wastewater solutions using natural adsorbent (chitosan)
were carried out in batch mode. The equilibrium data for the batch adsorption of
Cr(VI) onto chitosan were tested with Langmuir, Freundlich, and BET isotherm
models. The kinetics of Cr(VI) adsorption onto natural adsorbents was analyzed
using the pseudo-first-order, pseudo-second-order, and Elovich models.

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Materials and Methods

Experimental P rocedure
Characterization of Chitosan
Surface area analysis of the chitosan was carried out using BET apparatus (Porous
Materials, Inc., Analytical Services Division, New D elhi, India). The sample outgassed to 20 microns vacuum at 20 C, the instrument temperature 25 C, and the
testing temperature 195.76 C.
The surface morphology of the adsorbent was examined using a scanning electron microscope (SEM; Hitachi SU 6600, Japan). F or SEM, the samples were gold
sputtered, kept for 15 s, and observed at an accelerating voltage of 10 kV. Energy dispersive spectroscopy (EDS) studies were carried out to analyze the elemental composition of the adsorbent using an energy dispersive spectrophotometer (Horiba)
attached to SEM. The samples were analyzed at an accelerating voltage of 20 kV.
F ourier transform-infrared (F T-IR ) spectroscopy with attenuated total reflectance (ATR F T-IR ) was used to record infrared spectra (Jasco F T-IR 4100 system).
The sample and KBr were previously ground and dried at 120 C in a vacuum oven
for 2 h. Then, the mixture was squeezed to form transparent pellets which could be
measured directly. The broad peak around 3400 cm 1 was attributed to the OH
group and -NH group. The small peak observed at 2921 cm 1 corresponds to the
CH stretching group. The residual metallic ion concentrations were determined
using an atomic absorption spectrophotometer (AAS; Thermo Scientific AA 303).
The analysis was done by comparing the observed absorption with the one obtained
by suitable standard samples of the analyte under similar experimental conditions,
i.e., a calibration curve method was generally employed.
The extent of chitosan deacetylation was determined by titration with 0.01 M
NaOH (Bhole et al., 2004). The acetyl percentage was determined from the equation:
% Acetyl V

0:04305=W

where V is the corrected volume of NaOH and W is the weight of the sample. The
degree of deacetylation was calculated using the equation:
% Deacetylation 100

% acetyl

The viscosity of chitosan was determined using a Brookfield digital rheometer

(M odel H ADV-E) at 25 C. And the molecular weight of the chitosan was determined

Adsorption of Cr( VI) on Chitosan

837

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by the viscometric method (Khalaf, 2004) and following the Mark-HouwinkSakurada (MHS) equation (Beppu, 1999): g 1:57 10 4 M v0:79 , where g is intrinsic
viscosity and M v is the viscosity average molecular weight.
Batch Studies
Adsorption tests of Cr(VI) onto chitosan were carried out at different metal concentrations, adsorbent concentrations, contact times, shaking speeds, pH values, and
temperatures. Borosil glass conical flasks of 250 mL capacity with 50 mL of wastewater of desired Cr(VI) concentration and pH were used. Biosorbents were added
per dose requirements and subsequently the flasks were shaken at a constant rpm
in an incubator. The flasks were taken out from the shaker at predetermined intervals and the content was filtered using Whatman No. 1 filter paper. The filtrate
containing residual Cr(VI) was analyzed using AAS. Equilibrium data obtained in
batch studies are shown in F igure 1. The physicochemical analysis of adsorbents
before and after adsorption examined using SEM, EDS, and F T-IR is represented
in F igures 25. The characteristic parameters of chitosan are given in Table I.

Figure 1. (a) Effect of adsorption capacity (mg=g) on equilibrium concentration, mg=L, (b)
effect of adsorption capacity (mg=g) on time (min), (c) effect of pH on Cr(VI) adsorption,
(d) Langmuir plot, and (e) pseudo-second-order plot.

838

S. Bhuvaneshwari and V. Sivasubramanian

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Figure 2. SEM images of chitosan before and after adsorption.

Figure 3. ED S spectra of chitosan before and after adsorption.

Figure 4. IR spectrum of chitosan before adsorption.

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Adsorption of Cr( VI) on Chitosan

839

Figure 5. IR spectrum of chitosan after adsorption.

Table I. Physico-chemical characteristics of the chitosan

Characteristic
Chemical name
Empirical formula
Appearance
Particle diameter
Viscosity
Degree of deacetylation
Moisture
Ash
BET surface area
Langmuir surface area
Surface functional groups (F T-IR )

Total pore volume

Porosity based on skeletal density
(2.8000 g=cc)
Avg pore diameter (4 V=S)
Pore diameter (based on pore volume)
Pore diameter (based on surface area)
Elemental analysis (EDS)

Value
(1,4)-2-Amino-2-desoxy-beta-D-glucan
(C6H 11N O 4)n
Light yellow flake
110 mm
304 cps (1%)
80.79%
9.34%
0.25%
6.356 m 2=g
6.472 m 2=g
OH group, -NH group, CH
Before adsorption

After adsorption

0.0180 cc=g
0.0480 per gram
of sample

113.3634 A

117.651927 A

59.009625 A
C, 53.5%
O, 43.7%
Au, 2.8%

0.0113 cc=g
0.0254 per gram
of sample
110.3741 A

142.347419 A

58.241592 A
C, 37.88%
O, 44.08%
Cr, 15.55%
Au, 2.5%

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840

S. Bhuvaneshwari and V. Sivasubramanian

Continuous Studies
The fixed-bed column was made of an acrylic tube of 1.1 cm inner diameter and 12 cm
height. The column performance of Cr(VI) adsorption was studied using chitosan as
adsorbent at different bed heights (39 cm), flow rates (50200 mL=min), pH values
(37), temperatures (30 60 C), and initial metal concentrations (210 mg=L). The
chitosan weights taken were 0.6, 1.2, and 1.8 g for the bed heights of 3, 6, and
9 cm. Cr(VI) solution was pumped through the column in a down-flow direction by
a speed variable pump. Samples of the outlet bulk solution were collected at regular
time intervals, and their concentration for residual chromium was determined by
AAS. The outlet bulk solutions were recycled back into the sample reservoir
tank so that there was a continuous adsorption of chromium ion (Selvaraju and
Pushpavanam, 2009). A maximum adsorption capacity of 99.2% was observed in
the recycle process. The exhausted chitosan bed was regenerated using 0.1 M
H 2SO 4 as eluant at a flow rate of 50 mL=min, and the bed was flushed with distilled
water many times before the next set of experiments (Maji et al., 2007).
Adsorption Isotherm
Adsorption isotherms, known as equilibrium data, are the fundamental requirements
for the design of adsorption systems. The Langmuir, Freundlich, and BET isotherms
are the most frequently used to describe the adsorption equilibrium (Wan Ngah et al.,
2004). Adsorption is a time-dependent process, and hence it is very important to
know the rate of adsorption for the design and evaluation of the adsorbent efficiency
in removing the adsorbate from wastewater. Several models have been applied
to simulate the breakthrough curves to predict the scaling-up of a unit plant
(Zhou et al., 2004).
Langmuir Isotherm
The Langmuir adsorption isotherm is probably the most widely applied. The
assumption made in the Langmuir adsorption isotherm model is that all adsorption
sites have equal affinities for adsorbate molecules and that the presence of adsorbed
molecules at one site does not affect the adsorption of molecules at an adjacent site.
It is a semi-empirical isotherm derived from a proposed kinetic mechanism and is
based on four assumptions:
1. The surface of the adsorbent is uniform, that is, all the adsorption sites are
equivalent.
2. Adsorbed molecules do not interact.
3. All adsorption occurs through the same mechanism.
4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate
do not deposit on any other, already adsorbed, molecules of adsorbate. (Adsorption
happens only on the free surface of the adsorbent.)
The Langmuir isotherm is nevertheless the first choice for most models of adsorption
and has many applications in surface kinetics (usually called LangmuirHinshelwood kinetics) and thermodynamics. The linear form of the Langmuir
isotherm is
1
1
1

q e k L q max C e

1
q max

Adsorption of Cr( VI) on Chitosan

841

From the plot of q1 versus C1e , the constants qmax and kL can be determined from the
e
slope and intercept respectively.
Freundlich Isotherm
The F reundlich equation is an empirical relationship that describes the adsorption of
solute from liquid to solid surface and assumes that the stronger binding sites are
occupied first and the binding strength decreases with increasing degree of site occupation. The Freundlich isotherm is expressed generally as:
1

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q e kF C ne

At low pressures, the extent of adsorption is independent of pressure. However, at

high pressures it is dependent on pressure. Experimentally it has been determined
that the extent of adsorption varies directly with pressure until saturation pressure
is reached. Beyond that point the rate of adsorption saturates even with higher pressures. Thus, the F reundlich adsorption isotherm fails at higher pressures, which is its
limitation.
Brunauer-Emmett-Teller Isotherm
The concept of the Brunauer-Emmett-Teller (BET) isotherm is an extension of the
Langmuir theory. The latter is generally used for monolayer molecular adsorptions,
whereas the former is used for multilayer adsorptions with the following hypotheses:
(a) gas molecules physically adsorb on a solid in layers infinitely, (b) there is no interaction between each adsorption layer, and (c) the Langmuir theory can be applied to each
layer. The BET theory aims to explain the physical adsorption of gas molecules on a solid
surface and serves as the basis for the measurement of specific surface area of a material.
The resulting BET equation in linear form is expressed as

C 0

Ce
1
B 1 Ce

C e q e
Bqm
Bq m C 0

The plot of C CeC e q e versus CC e0 should give a linear relationship from which qm
0
and B can be determined from the slope and intercept of the plot, respectively.
Adsorption Dynamics
The study of adsorption dynamics describes the solute uptake rate and evidently this
controls the residence time of adsorbate uptake at the solid-solution interface. The
kinetics of Cr(VI) adsorption on chitosan was analyzed using pseudo-first-order,
pseudo-second-order, and Elovich kinetic models (Shokoohi et al., 2009). The
conformity between experimental data and model values is expressed by correlation
coefficients (R 2, values closer or equal to 1).
Pseudo-First-Order Equation
This is a second-order reaction expression in which one of the reactants is present in
great amounts and its effect is not seen. Thus the second-order rate equation has
been reduced to a pseudo-first-order rate equation. The linear form of the pseudofirst-order equation is generally expressed as:
log q e

q t log q e

k1

t
2:303

842

S. Bhuvaneshwari and V. Sivasubramanian

The plot of log (qe qt ) versus t should give a linear relationship from which k 1
and qe can be determined from the slope and intercept of the plot, respectively.
Pseudo-Second-Order Model
Applicability of second-order kinetics was tested using the pseudo-second-order
kinetic rate equation as:
dq
k 2 q e
dt

q t 2

The linear form of the pseudo-second-order equation is generally expressed as:

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t
1
t

2
qt k2qe qe

The plot of (t=qt ) versus t should give a linear relationship from which qe and k2 can
be determined from the slope and intercept of the plot, respectively.
Elovich Model
The Elovich kinetic equation is based on adsorption capacity and is generally
expressed as
dq
a exp bqt
dt

The constants a and b are determined from the slope and intercept of the linear
relationship of Equation (7).
Adsorption Column Design
Many different approaches are available for the design of adsorption columns. In
general, partial differential equations can be written incorporating the different mass
transfer and adsorption mechanisms. Typically, these models are complex and
require numerical solutions. Other models rely on experimental data and are simpler
to interpret. These models can be used to size the columns by determining the depth
of adsorption zone, the shape of the breakthrough curve, the time at break point,
and the amount of pollutant removed at break point (Yahaya et al., 2011).
Column Adsorption Kinetics
The column adsorption kinetics was studied by determining the mass transfer
coefficient according to the Adams-Bohart equation as:
lnC t =C 0 k C i t

k qv

z
ui

A straight line was attained for this system by plotting ln (C t=C 0) against t, as seen
in F igure 6 (Zhang et al., 2005), which gives the value of k from the slope of
the line. The mass transfer coefficient for the experimental system was 1.33
10 3 L=(mg min).

Adsorption of Cr( VI) on Chitosan

843

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Figure 6. Estimation of mass transfer coefficient for adsorption of Cr(VI) on chitosan.

Adsorption Models
Adsorption models are used to predict breakthrough curves of adsorption systems
and capacity of adsorbent. The three models examined in the present work are the
Adams-Bohart, Thomas, and mass transfer models.
Adams-Bohart Model. The Adams-Bohart model is used for the description of
the initial part of a breakthrough curve. The Adams-Bohart expression is
Ct
Z
exp K AB C O t K AB N O
Co
F
The linear form of the Adams-Bohart expression is
ln

Ct
Co

exp K AB C O t

K AB N O

Z
F

10

where KAB is the kinetic constant (L=mmol min), F is the linear flow rate (m=h), Z is
bed height (m), N 0 is the saturation concentration (mmol=L), and t is time (h) (Trgo
et al., 2011). Parameters describing the characteristic operations of the column (KAB
and N 0) were calculated using linear regression analysis. From a linear plot of ln
(Ct =C 0) against time (t), values of KAB and N 0 were determined from the intercept
and slope of the plot (F igure 7).
Thomas M odel. The Thomas model is used to calculate the adsorption rate
constant and solid phase concentration of adsorbate on the adsorbent through
continuous mode studies. This model assumes plug-flow behavior in the bed and
uses the second-order reversible reaction kinetics and Langmuir isotherm for
equilibrium. The model has the form:
Ct
1

K
C o 1 exp t q m
r

C o V

11

Substituting t V=r in Equation (11), it becomes:

Ct

Co

1
1 exp K t

12
qm
r

C o tg

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844

S. Bhuvaneshwari and V. Sivasubramanian

Figure 7. Breakthrough curve for Adams-Bohart model at 9 cm bed height (50 mL=min flow
rate).

It can be rewritten as:

Kt

qm
r

Co t ln

Ct
Co

13

This is in the form of

Y b

at

14

Constants KT and q were determined from a plot of lnC t =C 0 1 against t (Ramesh

et al., 2011). The experimental and predicted breakthrough curve are given in
Figure 8.
Mass Transfer Model. It is possible to predict the theoretical breakthrough curve
using data obtained from batch isotherm studies, which can be compared with the
experimental breakthrough curve. Langmuir isotherm data were used for preparing
the theoretical breakthrough curve, as it showed better fit (R 2 0.952) in batch isotherm studies. The detailed calculations (for initial Cr(VI) concentration of 6 mg=L
and at different breakthrough concentrations) are as follows:
1. The equilibrium line was prepared (figure not shown) assuming various values of
Ce and calculating the corresponding values of qe using Langmuir isotherm data
represented by:
qe

142:84 C e
1 4 Ce

15

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Adsorption of Cr( VI) on Chitosan

845

Figure 8. Breakthrough curve for Thomas model at 9 cm bed height (50 mL=min flow rate).

Langmuir parameters qmax and KL used here were obtained from the batch
isotherm study results.
2. An operating line was drawn that passes through the origin and the point (C 0, qe),
where C 0 6 mg=L and qe is the value corresponding to C 0 as per Equation (15).
3. The rate of transfer of solute from the solution over differential depths of column
is given by:
F w dC kC

C o dH

16

The term (C C ) is the driving force for adsorption and is equal to the distance
between the operating line and equilibrium curve at any given value of qe. Integrating
Equation (16) and solving for the height of adsorption zone:
Fw
hZ
Ka

CE

CB

dC
C

17

In the plot of (C C ) 1 versus C, the area under the curve represents the value of
the above integration for any value of h < hz, corresponding to a concentration C
between C B and C E . Equation (17) can now be written as:
Fw
h
Ka

CB

dC
C

18

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846

S. Bhuvaneshwari and V. Sivasubramanian

Figure 9. Experimental and predicted breakthrough curves at 9 cm bed height (50 mL=min
flow rate) (mass transfer model).

D ividing Equation (17) by Equation (18) now results in

Fw
Ka

C
R

h
C
CB
h z F w RE
Ka

CB

dC
C C

dC
C C

V
V

VB
VE

19

Now the plot of C=C 0 versus (V VB)=(VE VB) represents the theoretical breakthrough curve. The experimental breakthrough curve for 9 cm bed depth (at an
initial Cr(VI) concentration of 6 mg=L) at a flow rate of 50 mL=min was compared
with the theoretical breakthrough curve developed using the mass transfer model in
Figure 9. All the curves showed good correlation for removal of Cr(VI) from an
aqueous environment.

Result and Discussions

Adsorption Isotherm Study
In the present study, three equilibrium models were analyzed to investigate the suitable
adsorption isotherm, as seen in Table II. According to R2 values, both Langmuir and
Freundlich isotherms fit well for adsorption of Cr(VI) on chitosan. In the case of the
Freundlich isotherm, the adsorption intensity (n) values should be between 1 and 10
for a favorable isotherm (Nagashanmugam and Srinivasan, 2011). The adsorption
intensity (n) values were less than 1 in most of the cases studied, which shows that
adsorption of Cr(VI) onto chitosan is not favored based on the Freundlich isotherm.
The mechanism of Cr(VI) adsorption from synthetic wastewater by chitosan
fitted well with the Langmuir model, with a maximum adsorption capacity of
35.7 mg=g and R2 0.952 (Table II). In order to predict the adsorption efficiency
of the adsorption process, the dimensionless equilibrium parameter was determined
using the following equation:
r

1
1 kL C o

20

847

qmax, mg=g
KL, L=mg
R2
n
Kf
R2
B
qmax, mg=g
R2

Langmuir

1.048
0.63
0.926
0.113
0.553
0.986
2.82
1.09
0.915

2
3.26
1.207
0.923
0.26
73.33
0.977
6.21
3.74
0.836

3
8
1.62
0.936
0.455
121.0
0.978
7.92
1.18
0.798

4
12.35
1.14
0.943
0.55
60.28
0.984
5.27
17.25
0.825

Isotherms obtained at 30 C, pH 27.

Isotherms obtained at 30 60 C, pH 4.
c
Isotherms obtained at 30 C, pH 4, adsorbent dosage 1070 mg.

BET

Freundlich

Parameters

Model

pH a

11.11
0.978
0.961
0.53
43.59
0.989
4.27
15.61
0.861

6
5.75
0.96
0.862
0.388
33.95
0.929
4.48
7.69
0.684

7
8.54
0.409
0.889
0.396
5.45
0.944
29
34.48
0.519

30

40
27.03
0.822
0.794
1.34
12.56
0.710
10.66
31.27
0.181

50

Temperatureb

20.41
0.25
0.862
0.566
7.06
0.826
3.36
21.26
0.473

Table II. Isotherm parameters for Cr(VI) adsorption onto chitosan at different conditions

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25.6
1.95
0.94
1.59
18.3
0.90
28
35.7
0.55

60

35.7
4
0.952
1.87
29.4
0.940
38.04
24.5
0.922

Adsorbent dosagec

848

S. Bhuvaneshwari and V. Sivasubramanian

Table III. Dimensionless equilibrium parameter for
Cr(VI) adsorption onto chitosan
Cr(VI) concentration (mg=L)

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2
4
6
8
10

0.367
0.191
0.145
0.125
0.110

The r value for the initial concentration of 210 mg=L is presented in Table III.
Values of r < 1 represent favorable adsorption (Nagashanmugam and Srinivasan,
2011), which indicates a good agreement between experiment and Langmuir
isotherm parameters.

Adsorption Kinetics
In order to understand the kinetics of removal of Cr(VI) using chitosan as adsorbent,
pseudo-first-order, pseudo-second-order, and Elovich kinetic models were tested
with the experimental data. The correlation coefficient (R 2 0.999) and a close
agreement between experimental and calculated q values (qe,cal. 6.024 mg=g and
qe,exp 6.09 mg=g) indicate that the experimental data fit well with second-order
kinetic model, and hence it can be applied for the evaluation of Cr(VI) adsorption,
as illustrated in Table IV.

Effect of Bed Height on Adsorption Capacity

The effect of bed heights of 3, 6, and 9 cm on the breakthrough at a constant flow
rate of 50 mL=min was investigated (Tables VVII). Increase in adsorption capacity
with increase in bed height of the column has been attributed to improvement in
the surface properties of the adsorbent, which provides more binding sites for
adsorption (Singh and Pant, 2006). The breakthrough curves become sharper as
the bed height decreases from 9 to 3 cm. Both t b and t e increase with an increase
in bed height. This is in conformance with observations made elsewhere (F utulan
et al., 2011).

Table IV. Kinetic parameters for Cr(VI) adsorption on chitosan

Pseudo first order
qe
calculated
k1
(mg=g) (min 1)
0.99

0.017

Pseudo second order

R2
0.764

qe
k2
calculated (min 1 g
(mg=g)
mg 1)
6.09

0.074

Elovich

R2
0.999

a
b (g
(min 1g
mg 1)
mg 1)
4.78

4.2

R2

109 0.889

Adsorption of Cr( VI) on Chitosan

849

Table V. Parameters for Adams-Bohart model at different conditions

Flow rate
(mL=min)

Bed depth
(cm)

KAB
L=mmol h

No
mmol=L

Linear equation

R2

3
6
9
3
6
9
3
6
9

158.47
66.24
63.02
130.87
136.62
66.7
96.14
70.84
70.61

39.52
33.25
28.56
73.68
43.48
47.60
92.81
88.38
79.21

y 0.0689x 5.9519
y 0.0288x 4.1853
y 0.0274x 5.1306
y 0.0569x 4.557
y 0.0594x 5.6446
y 0.029x 4.5252
y 0.0418x 2.1167
y 0.0308x 2.9739
y 0.0307x 3.9853

0.712
0.743
0.828
0.729
0.78
0.753
0.738
0.798
0.74

50

100

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200

Effect of Flow Rate on Adsorption Capacity

The flow of influent varied from 50 to 200 mL=min for breakthrough analysis at a
constant bed height (9 cm). It was found that the maximum value of adsorption
capacity decreases with an increase in flow rate, as the residence time for contact
between adsorbent and adsorbate decreases (Han et al., 2009). The adsorbent usage
rates versus empty bed contact time are shown in F igure 10.

Effect of pH, Initial Metal Concentration, and Temperature

The pH of feed solution is an important controlling parameter in the heavy metal
adsorption process. In this work a pH range of 3.07.0 was studied, and the highest
maximum bed capacity and the longest breakthrough were obtained at pH 4.
Maximum bed capacity of Cr(VI) decreased with increase in the initial Cr(VI) concentration. F or different initial Cr(VI) concentrations (210 mg=L), the maximum
bed capacities were 64.44, 63.46, 62.24, 57.32, and 51.20 mg g 1 respectively. Also,
it was found that the break point time and bed capacities decreased as the temperature increased from 30 to 60 C (Aksu and Kutsal, 1991; Horsfall and Spif, 2005;
Tsezos and Volesky, 1987) (Table VII).
Table VI. Parameters for Thomas model at different conditions
Bed depth (cm)
3
6
9
3
6
9
3
6
9

F low rate (mL=min) r

Kt (L=mg min)

q (mg=g)

R2

50
50
50
100
100
100
200
200
200

0.012
0.0078
0.003
0.008
0.003
0.004
0.0077
0.006
0.0033

28.44
38.61
37.41
33.96
24.42
25.24
21.36
18.88
19.09

0.863
0.860
0.832
0.846
0.959
0.910
0.868
0.862
0.876

850

S. Bhuvaneshwari and V. Sivasubramanian

Table VII. Adsorption of Cr(VI) in a fixed bed column at different operating

parameters
Experimental parameters

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F low
q
q
rate
Bed
Initial
(mg=g) (mg=g)
R un mL= height Initial
Cr(VI)
Temperature
Thomas
no.
min (cm)
pH concentration
C
Exp.
M odel
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20

50
50
50
100
100
100
200
200
200
50
50
50
50
50
50
50
50
50
50
50

3
6
9
3
6
9
3
6
9
9
9
9
9
9
9
9
9
9
9
9

3
3
3
3
3
3
3
3
3
4
5
6
7
4
4
4
4
4
4
4

6
6
6
6
6
6
6
6
6
6
6
6
6
2
4
8
10
6
6
6

30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
40
50
60

59.98
63.20
65.56
58.65
48.91
39.50
33.82
26.52
24.77
62.24
59.11
43.30
34.55
64.44
63.46
57.32
51.20
56.66
52.87
47.75

28.44
38.61
37.41
33.96
24.42
25.24
21.36
18.88
19.09
35.41
33.28
27.66
24.34
38.76
37.28
33.54
30.03
32.22
29.43
25.56

Figure 10. Adsorbent usage rate at different flow rates.

R2

tb
min

0.863
0.860
0.832
0.846
0.959
0.910
0.868
0.862
0.876
0.822
0.834
0.846
0.812
0.841
0.834
0.837
0.826
0.814
0.832
0.831

35
55
85
25
40
60
10
25
50
80
75
65
50
85
80
65
45
70
55
40

Adsorption of Cr( VI) on Chitosan

851

Table VIII. Error of estimate values of different models

Model

F low rate (mL=min)

Bed height (cm)

Error of estimate

50

3
6
9
3
6
9
3
6
9
3
6
9
3
6
9
3
6
9

0.0577
0.0677
0.0797
0.0099
0.0114
0.0012
0.0302
0.0279
0.0031
0.0041
0.0039
0.0095
0.0029
0.0057
0.0072
0.0175
0.0036
0.0015

Mass transfer model

100

200

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Thomas model

50

100

200

Error Analysis
Error analysis was done to find the best model among those employed for the
present investigation. The error of estimate is given as:
SS

1
R
N

Ct
C0

Ct
C0

21
e

The errors between experiment and predicted models are shown in Table VIII. The
errors were found to be less than or equal to 0.03 for all the models (Kundu and
Gupta, 2006; Ramesh et al., 2011).

Conclusions
The adsorption of Cr(VI) onto chitosan was examined. The mechanism of Cr(VI)
sorption by chitosan gave a good fit with the Langmuir model with R 2 0.952
and a maximum q value of 35.7 mg=g. The values of r < 1 represent favorable
adsorption based on the Langmuir isotherm. SEM images after adsorption of Cr(VI)
confirms that Cr(VI) ions are deposited on the surface of the chitosan in a uneven
manner. The kinetics of Cr(VI) adsorption onto chitosan was well explained by
the pseudo-second-order kinetic model (R 2 0.999). Infrared spectroscopic studies
show that several functional groups (OH, CH, and -NH) are available on the
surface of the adsorbent for binding Cr(VI) ions. The IR spectra of the adsorbents
before and after adsorption of Cr(VI) are almost same, which clearly suggest the
processes as physisorption. The column performance of Cr(VI) adsorption onto
chitosan was found; maximum adsorption capacity increases with increase in bed
depth and decreases with increase in flow rate, Cr(VI) concentration, pH, and

852

S. Bhuvaneshwari and V. Sivasubramanian

temperature. The simulation studies for chromium adsorption onto chitosan were
carried out using linear regression analysis in MATLAB. Experimental values were
found to fit well with all three models. All three models were effectively simulated
and the model parameters were derived using MATLAB software. The simulation
studies produced better results for perturbation in the model parameters up to
20%. The results show that chitosan is an effective adsorbent for the removal of
Cr(VI) from wastewater in a fixed-bed column.

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Nomenclature
B
Cb
Ce
Ci
Ct
(C t=C 0)e
(C t=C 0)m
dt
Fw
k
KAB
kF
kL
Kt
k1
k2
m
n
N
N0
qe
qmax
qm
qt
qv
r
t
ui
v
V
V0
VB
VE
Z

BET constant
concentration of solute at breakthrough, mg=L
equilibrium concentration of adsorbate, mg=L
Cr(VI) concentration in aqueous solutions before adsorption, mg=L
instantaneous concentration of chromium leaving the bed, mg=mL
ratio of the effluent and the influent adsorbate concentrations
obtained through experiment
ratio of the effluent and the influent adsorbate concentrations
obtained through dynamic models
time interval, min
flow rate, mL=min
mass transfer coefficient, L=mg min
adsorption rate constant, L=mmol h, Adams-Bohart
F reundlich constant
Langmuir adsorption energy, L=mg
Thomas rate constant, L=min.mg
rate constant of pseudo first order, min 1
rate constant of pseudo second order, g=min mg
weight of adsorbent, g
F reundlich constant
number of the experimental point
adsorption capacity, mmol=L, Adams-Bohart
equilibrium adsorption capacity, mg=g
monolayer adsorption capacity of adsorbent, mg=g, Langmuir
maximum adsorption capacity, mg=g, BET
adsorption capacity at time t, mg=g
volume of chromium up taken by adsorbent, mg=L
dimensionless equilibrium parameter
time, min
linear flow rate of solution, mL=min
linear flow velocity of feed to bed, cm=h
volume of the bed, m 3; volume of water treated at time t, L
volumetric flow rate through the bed, mL=min
break point volume, L
exhaustion volume, L
bed height, cm

Greek letters
a
Elovich adsorption rate constant, mg=g min
b
Elovich desorption constant, g=mg

Adsorption of Cr( VI) on Chitosan

e
s

853

void fraction of the bed, m 3=m 3

time required for a 50% adsorbate breakthrough, min

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