International Journal of Biological Macromolecules 93 (2016) 408–417

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Removal of Pb(II) ions by using magnetic

chitosan-4-((pyridin-2-ylimino)methyl)benzaldehyde Schiff’s base
Gutha Yuvaraja a,∗ , Munagapati Venkata Subbaiah b
a
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China
b
Department of Environmental Science and Engineering, Ewha Womans University, 11-1 Daehyun-Dong, Seodaemun-Gu, Seoul 120-750, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: A novel crosslinked magnetic chitosan-4-((pyridin-2-ylimino)methyl)benzaldehyde Schiff’s Base

Received 2 June 2016 (m-CSPIB) was prepared by crosslinking of magnetic iron oxide nanoparticles with chitosan-4-((pyridin-
Received in revised form 26 August 2016 2-ylimino)methyl)benzaldehyde schiff’s base and used as an biosorbent for the removal of Pb(II) ions from
Accepted 30 August 2016
aqueous environment. The biopolymer has been characterized by XRD, FT-IR, SEM, TEM, 1 H NMR and VSM
Available online 31 August 2016
analysis. Kinetic studies were performed, and the data were fitted well with the pseudo-second-order
model. The equilibrium data followed Langmuir isotherm model and the maximum monolayer sorption
Keywords:
capacity was found to be 104.16 for Pb(II) ions at 323 K. Different thermodynamic parameters namely,
Chitosan
Terephthalaldehyde
change in Gibbs free energy, enthalpy change, and entropy changes were also evaluated from the tem-
2-amino pyridine perature dependence, and the results suggested that the sorption of Pb(II) onto m-CSPIB was feasible,
spontaneous and endothermic in nature.
© 2016 Published by Elsevier B.V.

1. Introduction amount of sludge, high cost, high energy input, and large quantities
of chemical reagents or poor treatment efficiency at low metal con-
Heavy metals are stable and persistent to environmental con- centration. Among these methods adsorption seems to be a more
taminants because they cannot be degraded. Among all the existing suitable method for the removal of heavy metals, due to its low
metals Pb(II) is one of the most hazardous, because it cannot be cost, simply operating, and high efficiency.
detoxified biologically and is toxic for most life forms. Lead is Chitin and its deacetylated derivative chitosan are natu-
widely used in industrial applications, such us battery, printing, ral polymers composed of randomly distributed ß-(1-4)- linked
pigments, fuels, photographic materials, and explosives manufac- D-glucosamine (deacetylated unit) and N-acetyl-d-glucosamine
turing. The permissible level of lead in drinking water is 0.05 mg L−1 (acetylated unit). Chitin is insoluble in aqueous media while chi-
[1]. The toxicological effects of lead in humans include inhibition tosan is soluble in acidic conditions due to the free protonable
of hemoglobin formation (anemia), sterility, hypertension, learn- amino groups present in the D-glucosamine units. Due to their nat-
ing disabilities, kidney damage and mental retardation [2,3]. Hence ural origin, both chitin and chitosan cannot be defined as a unique
the removal of lead from water is essential to protect human and chemical structure but as a family of polymers which present a high
environmental health. variability in their chemical and physical properties. Chitosan is
Efforts are made to develop effective and efficient technolo- an antibacterial, biocompatible, environment friendly, biodegrad-
gies for the removal of metal ions from aqueous solutions and able material and it is used in many fields of interest such as
wastewaters. A number of methods such as chemical precipitation pharmaceutical and medical applications, environmental protec-
[4], coagulation [5], membrane separation process [6], adsorption tion, textiles, wastewater treatment and agriculture [11]. From
and biosorption [7], osmosis [8], ion exchange [9], photo catalytic the structural point of view, the amino and two hydroxyl groups
degradation and biological methods have been applied for the on each glucosamine repeating unit can act as reactive sites for
removal of metal ions from water and wastewater [10]. The dis- chemical modification [12]. Chemical modification of chitosan is of
advantages of conventional methods such as production of large interest because the modification would not change the fundamen-
tal skeleton of chitosan, would keep the original physicochemical
and biochemical properties and finally would bring improved prop-
erties [13]. For biomedical applications water soluble complexes of
∗ Corresponding author. chitosan [14], biocompatible and biodegradable hybrid hydrogel
E-mail addresses: [email protected], [email protected] (Y. Gutha).

http://dx.doi.org/10.1016/j.ijbiomac.2016.08.084
0141-8130/© 2016 Published by Elsevier B.V.
 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417 409

[15], cationic hybrid hydrogels [16] and degradable controlled- terephthalaldehyde and it was represented in Scheme 1a. A cer-
release polymers and polymeric nanoparticles [17] have attracted tain amount of pyridine-2-amine (2 g) was dissolved in 30 mL
wide interest for controlled drug release because of their biocom- of ethanol. To this, a solution of terephthalaldehyde (2.81 g) in
patibility, high water content, organic solvent free environment methanol (40 mL) and 3–5 drops of acetic acid was added drop
and permeability towards molecules. wise with continuous stirring at room temperature. After that the
Chitosan based or modified chitosan adsorbents have been reaction mixture was refluxed under water bath for 2–4 h. Then,
found potential applications in wastewater treatment to remove the mixture was cooled and poured into a crushed ice. A yellow
metal ions from water due to the presence of high amino acids and precipitate was collected by filtration through Buchner funnel. The
polysaccharide (the compounds consisting lot of carboxyl, hydroxyl precipitate was recrystallized by water and kept in an oven for
and amino groups). The potential use of some chitosan modified further modification with chitosan.
adsorbents such as chitosan coated sand [18], chitosan crosslinked
with epicholohydrin-triphospate [19], vanillin-modified chitosan 2.4. Preparation of
[20] chitosan coated PVC beads [21], chitosan coated alumina [22], chitosan-4-((pyridin-2-ylimino)methyl)benzaldehyde schiff’s
carboxyl grafted chitosan [23], crab and arca shell biomass [24] and base (CSPIB)
chemically modified fluted pumpkin [25] used for the removal of
metal ions from wastewater. Recently new heterocycle and hydro- In the present study chitosan modification may occur through
gel modified chitosan adsorbent materials [26,27] have been used the free amino groups at C2 position of chitosan with an active
for the removal of heavy metal ions from aqueous systems. carbonyl compound such as terephthalaldehyde and it was pre-
The main objectives of this study are; (i) preparation sented in Scheme 1b. Freshly prepared chitosan beads were
of a novel crosslinked magnetic chitosan-4-((pyridin-2- suspended in 30 mL of methanol. To this 4 g of 4-((Pyridin-2-
ylimino)methyl)benzaldehyde schiff’s base (m-CSPIB), (ii) ylimino)methyl)benzaldehyde Schiff’s base (30 mL of methanol)
characterization of the adsorbent, (iii) to study the sorption was added. After that, the mixture was stirred with a mechani-
kinetics and (iv) to investigate the sorption process by Langmuir cal stirrer at 600 rpm for 3 h at room temperature. The obtained
and Freundlich models and the thermodynamic properties of the product appears to be a light yellow colored. The resulting light yel-
adsorbent. low colored beads were removed from the solution, washed two
times with distilled water then methanol. The obtained product
2. Materials and methods was named as CSPIB for further representation.

2.1. Materials 2.5. Preparation of cross-linked magnetic

chitosan-4-((pyridin-2-ylimino)methyl)benzaldehyde schiff’s
All the chemicals used in the present study were of ana- base (m-CSPIB) resin
lytical grade and were not further purified. Terephthalaldehyde,
2-aminopyridine, acetic acid, ammonium hydroxide, and sodium Fe3 O4 nanoparticles were synthesized by co precipitation of
hydroxide were purchased from Sigma-Aldrich PVT. Ltd. Double ferric and ferrous salts under the hydrothermal conditions. The
distilled water was used throughout the study and the stock solu- amount 6.4795 g of FeCl3 ·6H2 O and 3.3339 g of FeSO4 ·7H2 O were
tions were subsequently diluted with distilled water. dissolved into 150 mL of deoxygenated distilled water. Then the
solution of the mixture was stirred for 30 min. Chemical precipita-
2.1. Preparation of metal stock solution tion was achieved at room temperature under vigorous stirring by
adding 20 mL of NH3 ·H2 O solution (28%, v/v). During the reaction
Stock solution of Pb(II) was prepared by dissolving the accu- process, pH was maintained at about 10 and it was kept at 70 ◦ C
rately weighed amount of lead nitrate in double distilled water by for 1 h. The Fe3 O4 nanoparticles were separated with the power-
making the volume upto 1000 mL in volumetric flask. Stock solu- ful magnets, and then the precipitate (black color precipitate) was
tion was slightly acidified with 2–3 drops of concentrated HNO3 thoroughly washed with water and dried in a vacuum at 340 K.
to avoid precipitation. Fresh dilutions were prepared and used for The preparation of cross-linked magnetic CSPIB resin was car-
each experiment. ried out according to the following procedure. CSPIB (5 g) was
dissolved in 2.0% aqueous acetic acid (200 mL). Then 5 g of mag-
2.2. Preparation of chitosan beads netite was added, the mixture was vigorously stirred 4 h at room
temperature. After finishing the reaction the gelatinous product
Chitosan solution was prepared by dissolving 5.0 g of chitosan was collected, washed with ethanol, water and dried in vacuum
flakes in 250 mL of 2% of acetic acid solution at room temperature oven at 310 K for 24 h. Finally the obtained product was coded as
and homogenizing the solution for 24 h. The viscous solution of chi- m-CSPIB for further representation. Generally the interaction of
tosan was added drop by drop through a syringe at constant rate, chitosan cross-links which cross-links with terephthalaldehyde via
into a beaker containing 0.5 N of NaOH and the chitosan beads were acetyl formation between the hydroxyl groups of the glucosamine
formed. The beads were allowed to stabilize in NaOH solution for units of chitosan and aldehyde groups of terephthaldehyde or
1 h at room temperature. The similar size of chitosan beads were through Schiff’s base formation between the unsubstituted free
controlled by the syringe needle. A magnetic stirrer was used to stir amino groups [28] of chitosan with aldehyde groups of terephtha-
the aqueous NaOH solution. The wet chitosan beads were inten- laldehyde as presented in Scheme 2a and b.
sively rinsed with distilled water then with methanol to remove
any remaining NaOH solution. 2.6. Instrumentation

2.3. Preparation of 4-((Pyridin-2-ylimino)methyl)benzaldehyde The XRD analysis is carried out with Cu K␣ radiation
schiff’s base (k = 0.1540 nm) and 2␪ ranges from 1 to 800 . Which functional
groups present in the chitosan and cross linked chitosan was
A general method was followed to synthesis the schiff’s identified by using FT-IR spectrometer (Thermonicolet-200 series,
base. 4-((Pyridin-2-ylimino)methyl)benzaldehyde Schiff’s base Germany). The surface morphology of the pure chitosan and cross
was prepared by the condensation of 2-aminopyridine with linked chitosan was obtained by using SEM analysis (Carl Zeiss, EVO
410 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417

(a) O
N

N
AcOH
N

NH 2
O

pyridin-2-amine Terephthalaldehyde

O
4-((pyridin-2-ylimino)methyl)benzaldehyde

(b)

OH OH

N
O O
O O
HO O HO O

N
NH 2 N
n n

Chitosan

O
4-((pyridin-2-ylimino)methyl)benzaldehyde N

Chitosan-4-((pyridin-2-ylimino)methyl)benzaldehyde

Scheme 1. Preparation of (a) 4-(Pyridin-2-yliminomethyl)benzaldehyde Schiff’s base and (b) CSPIB.

MA 15, and England). The size and morphology of the naked Fe3 O4 varied with the 30–90 ppm and at every 15 min. The thermody-
was determined using transmission electron microscopy (TEM, namic parameters were studied by change in the temperature by
Tecnai G2). The magnetic behavior of the nanocomposites was ana- 303, 313, and 323 K in a temperature controlled shaking incubator.
lyzed at room temperature with a vibrating sample magnetometer Each determination was repeated thrice and the results obtained
(VSM, LakeShore-7404). The pH of the solution was measured with were given in their average value. The amount of Pb(II) adsorbed
a pH meter (Digisum D1-7007, India). The Pb(II) ion concentration by the adsorbent at equilibrium was obtained using the equation:
was determined by Atomic Absorption Spectrophotometer (Shi-
madzu AA-6300, Japan) with the wavelength of 217 nm, slit width
0.2 nm, lamp current 30 mA and flame type Air-C2 H2 .
(Ci − Ce )V
qe = (1)
M
2.7. Batch adsorption experiments

Batch adsorption studies were carried out by mixing 0.5 gm of

adsorbent with 50 mL of 25 mg/L as initial lead metal ion concen- where, qe (mg/g) was the adsorption capacity at equilibrium, Ci
trations at pH 5. The contents in the flasks were agitated on a and Ce were initial and equilibrium concentration (mg/L) of Pb(II)
mechanical shaker with a speed of 180 rpm for 105 min of con- respectively, M (g) was the adsorbent dosage, and V (L) was the
tact time. For kinetic studies the metal ion concentrations were volume of the solution.
 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417 411

(a) H 2N
H 2N

O OH
O OH
O O
O

O O

O O

O O
O O
HO HO O

NH 2 NH 2

(b) OH
O

O
HO O
N
N

O
O OH

O
HO

Scheme 2. (a) Terephthaldehyde reacts with hydroxyl groups in chitosan and (b) Terephthaldehyde reacts with amino groups in chitosan.

3. Results and discussion

3.1. Characterization of the adsorbent

3.1.1. XRD analysis

The crystalline size and structural properties of the chitosan,
bare Fe3 O4 and m-CSPIB are revealed by using Powder X-ray
diffraction and it was shown in Fig. 1. The nature of the crystal
structure of a sorbent plays an important role in describing the
sorption capacity of an adsorbent. It was known that the diffraction
pattern of pure chitosan flakes (Fig. 1A) shows the characteristic
peaks at 2␪ = 10 and 22 suggesting the formation of inter- and intra-
molecular hydrogen bonds in the presence of free amino groups
corresponding to crystal structure of chitosan. The sic characteris-
tic diffraction peaks of Fe3 O4 at 2␪ = 30.08, 35.58, 43.3, 53.8, 57.3
and 62.5, were assigned to (220), (311), (400), (422), (333) and (440)
planes. All the diffraction peaks of bare Fe3 O4 (Fig. 1B) are indexed
with a face-centered cubic (fcc) structure (JCPDS no: 82-1533). At
the same time, it can be seen that (Fig. 1C) the strong characteris-
tic diffraction peaks of Fe3 O4 ((220), (311), (400), (422), (333) and
(440)) could be found in the pattern of m-CSPIB. In the present
study, the chitosan-crosslinked with Schiff base has different aro-
matic substituent groups in its structure. Thus, it seems that the
crystallinity can be regulated by the modification of substituent
groups in chitosan molecule. The present study indicates that the
treated chitosan is having less crystalline structure as compared to Fig. 1. X-RD spectra of (A) pure chitosan, (B) Fe3 O4 nanoparticles and (C) m-CSPIB.
pure chitosan.
412 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417

1067 cm−1 (may be assigned to the –C C– stretching vibration)

respectively [29]. The major bands for the chitosan crosslinked with
the Schiff’s base in (Fig. 2B) can be assigned as follows: The peak
at 3422 cm−1 is attributed to the stretching vibration of O H band.
The peak at 2920 cm−1 corresponds to the C H stretch vibration.
The peak at 1662 cm−1 corresponds to the imine bond (–C N–). The
imine bond formed during cross-linking involves NH2 groups of
chitosan [30] and CHO groups of Terephthalaldehyde. The peaks at
1436 cm−1 (C H stretch bending of CH2 group), 1087 cm−1 (bridge
C O C stretch). The broad band (Fig. 2C) at about 3400 cm−1
which are concerned with OH and NH stretching vibrations of
m-CSPIB. The band located at 2925 cm−1 is attributed to the −CH
symmetrical stretching vibrations. The significant shifts of these
specific peaks to the lower or higher wave numbers suggest chem-
ical interactions of CSPIB with the Fe3 O4 nanoparticles (Fig. 2C). The
decrease in the intensity of the broad peak at 3417 cm−1 could be
attributed to the cross-linking via acetalization reaction between
the hydroxyl groups of the glucosamine units of chitosan and alde-
hyde groups of terephthalaldehyde. The characteristic absorption
peak appears at 580 cm−1 (Fig. 2C) attributed to the Fe O bond,
confirming the existence of Fe3 O4 . From the above analysis it may
be concluded that m-CSPIB has hydroxyl, amine, and carbonyl
groups were present in abundance and these functional groups are
Fig. 2. FTIR spectra of (A) pure chitosan (B) CSPIB and (C) m-CSPIB. the major binding sites for metal ions, and forming stable com-
plexes by co-ordination.

3.1.2. FTIR spectral analysis

Fig. 2 shows the FTIR spectra of pure chitosan, crosslinked chi-
tosan, and m-CSPIB were recorded to determine the frequency 3.1.3. SEM analysis
changes in the functional groups in the adsorbent and the spec- Surface morphology of the adsorbent is the most important one
tra were measured within the range of 500–4000 cm−1 . The major and the adsorption capacity of the adsorbent mainly due to differ-
bands for the chitosan beads in (Fig. 2A) can be assigned as fol- ence in their surface structure and surface porosity. Fig. 3 shows the
lows: A characteristic and broad band appears around 3424 cm−1 , SEM images of chitosan flakes, Fe3 O4 nanoparticles and m-CSPIB.
revealing the stretching vibration of–NH or −OH groups in chi- Pure chitosan flakes shows the irregular surface with some crys-
tosan. 2922 cm−1 (–CH stretching vibration in −CH3 groups of the talline structure. The morphology of iron oxide nanoparticles is
chitosan), 1635 cm−1 (C O groups from the −COOH and ketones), spherical shaped and well distributed with aggregation. But in case
1382 cm−1 (–CH symmetric bending vibrations in CHOH–), of m-CSPIB an entirely different morphological structure emerged

Fig. 3. SEM images of (A) pure chitosan, (B) Fe3 O4 nanoparticles and (C) m-CSPIB.
 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417 413

investigated adsorption of Pb(II) at pH 2.0–8.0 (Fig. 7). In acidic

conditions (at low pH values) H+ ion concentration is very high and
there is a competition between H+ ions and the basic NH2 func-
tional groups which are present in chitosan. Due to this the metal
ion uptake capacity in acidic conditions is less may be attributed
to the protonation of the lone pair of nitrogen hinders the com-
plex formation. The abundant of H+ in the medium may leads to
another type of interaction (ion exchange mechanism) through
the protonation of the unsubstituted amino groups, and the for-
mation of the lead anions (PbCl3 − ) [31]. From Fig. 7 the removal
percentage of Pb(II) increased with increase in pH. The H+ ions
concentration decreases with increasing pH of the medium, more
number of Pb(II) get exchanged and hence the maximum adsorp-
tion capacity is observed at pH 5. This may be attributed to the
presence of free lone pair of electrons on nitrogen atoms suit-
able for coordination with the metal ion to give the corresponding
Fig. 4. TEM image of Fe3 O4 nanoparticles.
polymer–metal complex [32]. At pH value higher than 5, decreasing
tendency were observed and the adsorption studies could not be
carried out because of the precipitation of Pb(II) as Pb(OH)2 . Hence
and the sorbent surface was aligned in a non-uniform, rough surface
all the adsorption experiments were performed at pH 5.0.
and irregular way was observed.
3.3. Influence of adsorbent dose
3.1.4. TEM analysis
Transmission electron microscopy (TEM) has been used to iden- Adsorbent dose is one of the crucial parameter in adsorption
tify the size, shape and morphology of nanoparticles and it was process because it determines capacity of the adsorbent for a given
shown in Fig. 4. It reveals that the nanoparticles are well dispersed initial Pb(II) metal ion concentration from the solution. The dose
and predominantly spherical in shape with 100 nm size. of adsorbent was varied from 0.1 to 0.7 g, while keeping all other
experimental variables (viz. pH 5, initial metal ion concentration
3.1.5. 1 NMR analysis 30 mg/L, contact time 3 h and agitation speed 180 rpm/min) con-
The 1 H NMR spectra of the pure chitosan and CSPIB were shown stant. The Pb(II) ion removal percentage increases with increasing
in Fig. 5A and B. The 1 H NMR spectra of the pure chitosan exhibits adsorbent dosage. This can be attributed due to the greater avail-
the well resolved peaks at ␦ 4.80 – 1.80. After crosslinking of chi- ability of active sites and more functional groups on the surface of
tosan with the 4-(Pyridin-2-yliminomethyl)benzaldehyde Schiff’s the adsorbent material, result in a higher Pb(II) removal percentage
base it exhibits the prominent signals and significance differences and it was shown in Fig. 8. Beyond 0.5 g, there was no appreciable
in their chemical shifts. In CSPIB the aromatic peaks appeared increase in Pb(II) removal percentage, which indicates the satura-
between ␦ 8.62 − 6.6. Remaining peaks appeared at appropriate tion of active adsorption sites present in the biopolymer composite
region. Based on the above results and 1 H NMR spectra conform- through the adsorption reaction. Therefore, the optimum adsorbent
ing the crosslinking were occurred between the free amino groups dose of 0.5 g/L was selected for all the subsequent experiments.
at C2 position of chitosan with the aldehyde groups of terephtha-
laldehyde. The 1 H NMR spectra exhibits the well resolved signals 3.4. Effect of contact time and initial Pb(II) ion concentration
and significant differences in their chemical shifts of pure chitosan
and CSPIB. The influence of the initial metal ion concentration and the effect
of the contact time on Pb(II) removal were investigated using 30, 50,
3.1.6. VSM analysis 70, and 90 mg/L at various contact times (15–120 min). Percentage
The magnetization measurement of bare Fe3 O4 nanoparticles of metal removal increases with increasing initial concentrations
and the CSIPB resin were shown in Fig. 6. The magnetization of till certain maximum limit and them remains unaffected. The time
the Fe3 O4 (Fig. 6A) magnetic particles and m-CSPIB (Fig. 6B) resin it takes metal ions and adsorbent to reach equilibrium is of great
having the 67.56 and 29.6 and emu/g susceptibility values. The importance in adsorption experiment because it depends on the
magnetic susceptibility value (29.6 emu/g) of this adsorbent could nature of the system used. The removal rate of Pb(II) ions was
ensure a feasible application for the metal ion removals. As shown rapid at the beginning owing to the availability of sorption sites
in Fig. 6 Fe3 O4 nanoparticles can be attracted to the sidewall of the and it became slow because the available sorption sites are limited
bottle from the aqueous solution by applying a magnet, and finally with increasing the contact time. The removal of Pb(II) ions was
resulting the colorless and clear supernatant. The decrease in the increased with the increase in contact time (Figure not shown), the
magnetization in m-CSPIB may be due to the crosslinking of CSPIB maximum removal of Pb(II) ions was observed at 105 min of contact
and decreases the relative percentage of iron oxide in the sorbent. time. The main reason for this, driving force weakens and finally the
The decrease in saturation magnetization can be explained by sev- equilibrium is reached (105 min) and this is taken as an optimum
eral factors including size effect and particle crystallization. It can contact time for further experiments.
also be observed from this figure that magnetization moment of
Fe3 O4 nanoparticles decreases after crosslinking of magnetic par- 3.5. Adsorption kinetics
ticles on the surface of the CSPIB, meaning that chitosan does not
affect magnetic properties of this m-CSPIB. Kinetics is an important parameter for designing sorption
systems and is required for selecting the optimum operating condi-
3.2. Influence of solution pH tions for full-scale batch metal removal process. A number of kinetic
models have been developed to describe the kinetics of metals
The initial pH of Pb(II) is an important parameter to control removal. For elucidation of sorption kinetics, three kinetic models
the adsorption capacity of the sorbent. In the present study we such as, Lagergren’s pseudo-first-order [33], pseudo-second-order
414 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417

1
Fig. 5. H NMR spectra of the (A) pure chitosan and (B) CSPIB.
 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417 415

K2 (g/mg.min) and Kid (mg/g min−0.5 ) is the is the rate constant

of pseudo-first order, pseudo-second order, and intraparticle dif-
fusion models. The pseudo-first order kinetic constants (K1 ) and
the biosorption rate constant (K2 ) were determined from linear
plots of log (qe- qt ) versus t and t/qt versus t and the intraparticle
diffusion model coefficient values are calculated from the plot of
qt versus t0.5 values (Figures not shown). C is the intercept that
gives an idea about the thickness of the boundary layer in intra-
particle diffusion model. The K1 , K2 , Kid , and R2 values of the three
kinetics models were included in Table 1. As shown in Table 1 the
R2 values are very less in pseudo-first-order suggesting that the
biosorption of Pb(II) ions does not follow pseudo-first-order kinetic
model. The R2 values are close to unity (0.999) for all Pb(II) con-
centrations in pseudo-second order kinetic model. This indicates
that the pseudo-second-order model can be applied to predict the
adsorption kinetic data as the rate-controlling step. Most of the ear-
lier studies have reported that the adsorption of metal ions onto
Fig. 6. Magnetization curves of (A) bare Fe3 O4 nanoparticles and (B) m-CSPIB. the adsorbent surface follows pseudo-second order kinetic. It can
be deciphered that these plots have three distinct regions (intra-
particle diffusion model and the figure was not shown). The first
sharper portion is the transport of target ions from the bulk solu-
tion to the adsorbent surface. The second portion is the diffusion
of the target ions from the external surface into the pores of the
adsorbent. The third portion is the final equilibrium stage, where
the target ions were adsorbed on the active sites on the internal
surface of the pores and the intra-particle diffusion starts to slow
down due to the solute concentration getting lower and lower in
solution.
In addition, the sum of square error (SSE) test was carried out to
predict the best fit.
Fig. 7. Effect of pH on adsorption of Pb(II) onto m-CSPIB.
 (qt,e − qt,m )2
SSE = (5)
q2t,e
100
where qt,e and qt,m are the experimental biosorption capacities of
90 metal ions (mg/g) at time t and the corresponding values that are
obtained from the kinetic models and are shown in Table 1. Pseudo-
80 second-order model has the lowest SSE values when compared
with the pseudo-first-order and intraparticle diffusion models.
70
% Removal

Based on the low SSE values it may be concluded that pseudo-

60
second-order model is the best fit model for the experimental data.

50 3.6. Adsorption isotherms

40 The equilibrium adsorption isotherm is fundamental in describ-

ing the interactive behavior between solute and adsorbent, and it
30
is very important for designing the adsorption system. To quantify
the sorption capacity of Pb(II) ions onto m-CSPIB was interpreted
20
0.1 0.2 0.3 0.4 0.5 0.6 0.7 by, two-parameter equations namely Langmuir [36] and Freundlich
[37] isotherm models.
Amount of dose (g)
Langmuir isotherm describes the adsorption taking place in a
Fig. 8. Effect of sorbent dose on adsorption of Pb(II) onto m-CSPIB. monolayer; in other words, the adsorption can only occur at a fixed
number of definitive localized sites at the surface, and each one
[34] and intraparticle diffusion [35] models were applied to the these sites can adsorb only one molecule (monolayer). All sites
experimental sorption data. The linear form of the pseudo-first- are equivalent and no interactions between adsorbed and adjacent
order, pseudo-second-order and intraparticle diffusion models rate molecules take place. The linearized form of the Langmuir isotherm
equation is given as follows; is represented as follows:
1 1
1 1
K1 = + (6)
log(qe − qt ) = log qe − t (2) qe qm b Ce qm
2.303
t 1 1 where qe is the equilibrium metal ion concentration on the sorbent
= + t (3)
qt K2 q2 e qe (mg/g), Ce is the equilibrium metal ion concentration in the solution
(mg/L), qm is the monolayer biosorption capacity of the sorbent
qt = Kid t 0.5 + c (4)
(mg/g), and b is the Langmuir constant related to the free energy of
where qe and qt are the amount of the Pb(II) removal per unit mass sorption. The values of qm (mg/g), and b were calculated from the
of biosorbent (mg/g) at equilibrium and at time t (min). K1 (min−1 ), slope and intercept of 1/Ce versus 1/qe . The maximum monolayer
416 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417

Table 1
Kinetic parameters for the biosorption of Pb(II) onto m-CSPIB at different concentrations.

Pb(II) Conc. (ppm) Lagergren first order Pseudo-second-order Weber and Morris

K1 (1/min) R2 SSE K2 (g/mg min) R2 SSE Kid (mg/g min−0.5 ) R2 SSE

30 0.020 0.982 0.987 0.0048 0.999 0.1607 0.301 0.971 0.8222

50 0.027 0.985 0.990 0.0052 0.999 0.0354 0.466 0.962 0.8448
70 0.032 0.990 0.992 0.0039 0.999 0.0362 0.679 0.966 0.8433
90 0.036 0.992 0.992 0.0092 0.999 0.0146 0.244 0.974 0.9492

sorption capacity was found to be 104.16, mg/g of Pb(II) onto m- be due to the fact that the interaction between the Pb(II) ions
CSPIB. with m-CSPIB was stronger at higher temperatures. Higher uptake
Another parameter in the Langmuir isotherm a dimension less capacity at higher temperature is due to the increase in molecu-
separation factor (RL ) is defined as follows: lar diffusion or it may be attributed due to the availability of more
and more active sites on the surface of the biosorbent by the expan-
1
RL = (7) sion of the pores. The increase in adsorption percentage with rise in
(1 + bC0 )
temperature was attributed to the endothermic nature of the pro-
where C0 (mg/g) is the initial metal concentration, b is the Lang- cess and it was further explained by evaluation of thermodynamic
muir constant. For favourable biosorption, RL must lie within 0 to1, parameters.
where RL > 1, RL = 1 and RL < 0 indicate the unfavourable, linear and
irreversible biosorption. In this study, the RL values lie between 0
and 1. This indicates a highly favorable adsorption and increasing 3.8. Thermodynamic study
adsorption efficiency at higher Pb(II) concentrations.
The Freundlich isotherm is another form of approach for the The biosorption process depends on the temperature and is
adsorption isotherm on heterogeneous surfaces. The Freundlich associated with several thermodynamic parameters. Thermody-
model is considered as multi-site adsorption, when the adsorbate namic parameters, such as of Gibbs free energy change (Go ),
surface has heterogeneity. The linearized form of the Freundlich enthalpy change (Ho ) and entropy change (So ) were used to
isotherm model is represented as below; evaluate the thermodynamic feasibility of the process and to con-
firm the nature of the biosorption process. The parameters were
1 determined by using the following the equations:
log qe = log Kf + log Ce (8)
n
where Kf (mg/g) is a constant relating the biosorption capacity and Go = −RT ln KL (10)
1/n is an empirical parameter relating the biosorption intensity. The
values of Freundlich constants Kf and 1/n are included in Table 2. H o S o
ln KL = − + (11)
The values of Freundlich constants Kf and 1/n obtained from plots RT R
of log Ce vs. log qe (Figure not shown) and the values are included
in Table 2. The 1/n values are found in the range of 0.541–0.664, where, R is the universal gas constant (8.314 J/mol K), T is the tem-
when the temperature was altered from 303 to 323 K. The 1/n val- perature (K) and KL is obtained by multiplying Langmuir constant
ues between 0 and 1 indicate that the biosorption of Pb(II) onto b and qm . The changes in enthalpy (Ho ) and entropy (So ) were
m-CSPIB is favorable under the conditions studied. For all cases, estimated from the slope and intercept of the plot of ln KL versus 1/T
the Langmuir equation fits the experimental data better than the (Figure not shown). The negative values Go was −6.009, −5.452
Freundlich isotherm. It is clear that the Freundlich model could not and −5.164 kJ/mol suggest that the sorption of Pb(II) onto m-
fit all the experimental data well, as R2 values are generally lower CSPIB is a spontaneous process and thermodynamically favourable
and the chi square values are higher than Langmuir model. under the experimental conditions. Increase in the values of Go
with increase in the temperature indicates that the adsorption of
Pb(II) was spontaneous. Generally the change in free energy for
3.6.1. Chi-Square analysis
physisorption is between −20 and 0 KJ mol−1 but chemisorptions
Chi square test was adopted in order to find the suitability of an
is arrange of −80 to −400 KJ mol−1 [38]. The values of Go sug-
isotherm that fits best the experimental data. The chi-square statis-
gest that the adsorption is mainly a physisorption process. Positive
tics is basically the sum of the squares of the difference between the
value of Ho (8.23 kJ/mol) suggest that sorption of Pb(II) onto m-
experimental and calculated data from models, with each squared
CSPIB is endothermic. The entropy (So ) of adsorption was found
difference is divided by corresponding data obtained by calculation.
to be positive (0.0437J/mol K) and this is indicative of increased
The equation for evaluating the best fit model is as follows:
randomness at the adsorbent solution interface.
 (qe − qe,m )2
2 = (9)
qe,m
3.9. Comparison with other adsorbents
where qe,m is the equilibrium capacity obtained from the model
(mg/g) and qe is the experimental equilibrium capacity (mg/g). The adsorption capacity of m-CSPIB for Pb(II) metal uptake is
From Table 2, lower 2 values of Langmuir isotherm model show mainly depend on the properties of adsorbent such as adsorbent
that the experimental data correlate well with the Langmuir structure, functional groups and surface area. The values are based
isotherm than the Freundlich isotherm. on Langmuir adsorption capacity. The experimental data of the
present investigation is compared (Table 3) with the reported val-
3.7. Effect of temperature ues in literature and the adsorption capacity of m-CSPIB is higher
than that of the majority of the adsorbents reported in literature
It is apparent that the uptake capacity (adsorption capacity) of [39–44]. Therefore, inexpensive and easily preparative m-CSPIB
the adsorbent increased from 74.62, 79.36 and 104.16 mg/g with composite can be used in place of more costly adsorbents for Pb(II)
increasing the temperature ranging from 303 to 323 K. This might removal.
 Y. Gutha, V.S. Munagapati / International Journal of Biological Macromolecules 93 (2016) 408–417 417

Table 2
Langmuir and Freundlich isotherm constants and correlation coefficients for Pb(II) biosorption onto m-CSPIB at different temperatures.

Temp. (K) Langmuir Freundlich

qm (mg/g) KL (L/mg) R2 ␹2 Kf (mg/g) 1/n R2 ␹2

303 74.62 10.86 0.999 13.36 13.21 0.541 0.989 67.35

313 79.36 8.12 0.999 16.56 10.54 0.561 0.990 98.30
323 104.16 6.84 0.999 36.57 7.87 0.664 0.991 151.87

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