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Journal of the Taiwan Institute of Chemical Engineers

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Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied

poly(methacrylate) nanoparticles: Dynamics, equilibrium and
thermodynamics studies
Medhat A. Shaker a,b,,
a
Chemistry Department, Faculty of Science, University of Jeddah, Jeddah, Saudi Arabia
b
Chemistry Department, Faculty of Science, Damanhour University, Damanhour, Egypt

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

Article history: Novel chitosan/methacrylic acid nanoparticles (100120 nm), CMA with superior adsorptive properties
Received 17 February 2015 (195340 mg/g) were fabricated by a polymerization reaction, characterized by FTIR, TEM, TGA and DSC
Revised 12 May 2015
methods and applied for removing Co(II), Ni(II) and Cu(II) ions from aqueous solutions using batch adsorp-
Accepted 17 May 2015
tion technique. The ionic adsorption activity and performance of CMA including isotherm, kinetics and ther-
Available online xxx
modynamics were comprehensively studied to establish related tting models. All parameters inuencing
Keywords: the removal eciency such as: adsorbent dose, pH, initial adsorbate concentration, contact time and tem-
Thermodynamics perature were considered to setup optimal adsorption conditions. The experimental data were tted well
Dynamics to the pseudo-second-order kinetic model and to Langmuir model which predicted different stoichiometric
Heavy metals adsorption temperature-independent sites (A, B and C) in CMA surface with variable capacities that bind selectively to
Chitosan-methacrylic acid metal ions. Thermodynamic data predicted endothermic, spontaneous and chemical adsorption process. The
Nanoparticles
recoveries of the adsorbed metal ions from CMA nanoparticles were 8590%, after three sorptiondesorption
cycles indicating a great promising application of CMA in metal treatments.
2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction of its high effectiveness, ease of operation, low operating cost, no

The massive discharges of heavy metal ions into aquatic envi-
ronments because of the increased anthropogenic activity and many
industries such as metal nishing, pulp, lead smelters, ceramics,
mining, electroplating and battery manufacturing result in an ele-
vated water contamination, which is extremely unsafe to the human
beings [1]. The abundant and persistent heavy metal ions can accu-
mulate in water habitats, living organisms, water fauna and ora,
enter the food chain and threat the human health causing cancer,
brain damage, lung damage, central nervous system damage, which
may lead to death [1,2]. Therefore, it is necessary to eciently remove
toxic metal ions from wastewaters before their release in the envi-
ronment. Numerous physical, chemical and biological [3] treatment
technologies have been reported for the removal of toxic metal ions
such as chemical precipitation [4], adsorption [510], ion-exchange
[11], electro coagulation [12] and membrane separation [13]. How-
ever, among those technologies, the adsorption technique has been
found to be the best technology for toxic metals removal because
Correspondence address: Chemistry Department, Faculty of Science, University of
Jeddah, Jeddah, Saudi Arabia. Tel.: +20453293011; fax: +966553471259.
Chemistry Department, Faculty of Science, Damanhour University, Damanhour,
Egypt.
E-mail address: drmashaker@yahoo.com, massayed@kau.edu.sa
http://dx.doi.org/10.1016/j.jtice.2015.05.027
1876-1070/ 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
generated poisonous byproducts and possible regeneration of adsor-
bents. Though various adsorbents such as chitosan, activated carbon,
carbon nanotubes, silica and many biopolymers have been used for
removing toxic metals ions from wastewaters, still there is a sus-
tained demand for developing ecient novel eco-friendly and cost
effective adsorbents for the same purpose. Chitosan (CS), a nontoxic
fully or partially de-acetylated product of chitin has a prime rank
as adsorbent for various heavy metal ions due to its many reactive
chelating groups [14]. If CS were to be used as ecient adsorbent it is
essential to be chemically modied so as to solubilize its crystalline
parts and make its ligating groups available for metal chelation.
Chemical modication resulting in the formation of chitosan-based
nanomaterials is anticipated to be promising because it can provide
access to a wide variety of novel hybrid materials with superior
adsorptive properties [9]. In this study, we report the synthesis of
novel nanoparticles, CMA made of CS and methacrylic acid, MA by
polymerization reaction that can easily adsorb Co(II), Ni(II) and Cu(II)
ions from aqueous solution with high removal eciency. Adsorption
experiments for metal ion removal were conducted to evaluate the
effectiveness of the new CMA in metal removal performance. The
effects of various equilibrium and analytical parameters such as
the pH, initial metal concentration, contact time, adsorbent dosage
and temperature on the adsorption capacity and rate were investi-
gated. Adsorption isotherms and kinetic models were employed to

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027
JID: JTICE
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2 M.A. Shaker / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 112
investigate the mechanism involved in the removal of the investi-
gated metal ions from aqueous solution. Desorption experiments
were also done to nd the cost-effectiveness of the adsorbent.
2. Experimental
2.1. Materials
Chitosan, CS (deacetylation degrees > 90% and average molecu-
lar weight 111 kDa) and other necessary chemicals such as K2 S2 O8 ,
methacrylic acid (MA), Cu(NO3 )2 3H2 O, Co(NO3 )2 4H2 O, Ni(NO3 )2 ,
HNO3 and NaOH used in this work were purchased from Sigma
Aldrich Chemical Co (St. Louis, USA). The pH of solutions was adjusted
by adding appropriate amounts of HNO3 or NaOH. All glassware was
washed with HCl acid (1.0 M) before and after each experiment to
avoid the binding to metals. Double distilled water was used through-
out the work.
2.2. Apparatus
The samples were separated by a centrifuge model 236HK
(Hermle, Germany). All pH measurements were measured using an
Orion pH meter model 420A (Thermo Scientic, USA). The FTIR
(4004000/cm) spectra were determined using a spectrophotome-
ter model 8400S (Shimadzu, Japan) and spectroscopic grade KBr
powder. A freeze-dryer model FDU (Operon, South Korea) used
to lyophilize CMA. Thermal studies were performed using TGA
model Q500 (TA Instruments, USA) within (20500 C) tempera-
ture range at heating rate of 10 C/min and nitrogen ow rate of
60 cm3 /min. DSC scans were conducted on Mettler Toledo Instrument
(Leicester, UK). All samples were run in triplicate. The size of nanopar-
ticles was measured using a particle size analyzer model NanoBrook
90Plus (Brookhaven Instruments Corporation, USA). The nanoparticle
morphology was observed using TEM model CM200 (Philips Scien-
tic, UK). The zeta potential of CMA nanoparticles was measured at
various pH values with a zeta potential analyzer model delta 440sx
(Beckman Coulter, USA). The residual concentrations of Cu(II), Co(II)
or Ni(II) ions in the adsorption experiments were determined using
an atomic adsorption spectrophotometer model PU9400 (Philips Sci-
entic, UK).
2.3. Preparation of CMA nanoparticles
CMA nanoparticles were synthesized by one-stage emulsion poly-
merization reaction [15] where 7 g of chitosan was dissolved into 1 L
of acetic acid solution (2% w/w), followed by the addition of 3 g of
MA. The mixture was heated to 70 C under continuous stirring in
a thermostated water bath and purged with nitrogen, then to this
solution, 0.3 g of K2 S2 O8 was added to initiate the polymerization
reaction and degrade the chitosan molecules till CMA nanoparticles
started to be formed. The formation of small size CMA nanoparticles
has been indicated by the opalescence in the resulting suspension.
The resulting suspension was cooled in an ice bath and centrifuged
(25 min, 6000 rpm) to separate the CMA nanoparticles with discard-
ing the supernatant. The CMA nanoparticles were re-suspended in
Millipore water, washed with acetone, then benzene, freeze-dried for
1 h and stored in a desiccator for adsorption experiments.
2.4. Adsorption experiments
A series of batch-mode contact experiments were performed in
125 mL stoppered bottles by agitating 50 mg of CMA adsorbent in
100 mL of known varied initial concentrations (0200 mg/L) of each
of Co2+ , Ni2+ and Cu2+ metal ions solutions in a thermostated shaker
(200 rpm) adjusted at pH of 6.0, 5.0 and 4.0 for the respective metal
Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027
[m5G;June 12, 2015;11:56]
ions and 20, 30, and 40 C. These batch experiments were also con-
ducted to explore the effects of medium pH, contact time, adsorbent
dose, initial adsorbate concentration and temperature on the inves-
tigated metal removal eciencies. The samples were centrifuged at
16,000 rpm for 10 min and the supernatants analyzed for the residual
metal ions concentration. All experiments were carried out in tripli-
cate and the mean values were used in the data analysis. The equilib-
rium amount of metal ions adsorbed onto CMA nanoparticles (metal
uptake capacity) was calculated by Eq. (1) while the metal removal
eciency R was calculated from Eq. (2).
(ci ce )V
qe = (1)
m
(ci ce )
R= 100 (2)
ci
where qe (mg/g) is the equilibrium amount of metal ions adsorbed
onto 1 g of the CMA surface (adsorption capacity), ci and ce (mg/L)
are the initial and nal equilibrium concentrations of metal ions, re-
spectively, V (L) is the volume of the solution of metal ions and m (g)
is the adsorbent mass.
2.5. Adsorption kinetics
Adsorption kinetics were investigated to evaluate the rate of Cu2+ ,
Co2+ and Ni2+ adsorption. The experiments were conducted using ini-
tial metal concentration of 100 mg/L, optimum pH for each metal ion,
50 mg of CMA adsorbent, shaking rate (200 rpm) and different tem-
peratures (293, 303 and 313 K). Adsorption rates were analyzed using
four kinetic models namely, pseudo-rst order, pseudo-second order,
modied Ritchies second order and intraparticle diffusion.
3. Results and discussion
3.1. Characterization of CMA nanoparticles
The positively charged amino groups of CS molecules in solu-
tion electrostatically interact with MA carboxyl groups to form CMA
nanoparticles, Fig. 1. FTIR spectroscopy was used to investigate the
structures of CS and CMA nanoparticles, Fig. 2a. In the FTIR spectrum
of CS , the basic characteristic bands of at 3455/cm (OH stretch over-
lapped with NH stretch), 2867/cm (CH stretch), 1654/cm (amide
C=O stretch), 1154/cm (bridgeO stretch), 1094/cm (CO stretch) and
620/cm (pyranoside ring stretch) have been recognized [16]. In the
FTIR spectrum of CMA, the C=O band at 1649/cm in CS disappeared
while new bands at 1638 and 1545/cm corresponding to COO and
NH3 + groups, respectively were observed suggesting successful ionic
interaction between CS and MA to form CMA. Moreover, the appear-
ance of bands at 1703 and 1264/cm (C=O) in CMA spectrum con-
rmed the presence of MA moiety in composition. The particle size
distribution curve for CMA is illustrated in Fig. 2b while the depen-
dence of this particle size on solution pH is shown in Fig. 2c. It is
observed that the CMA particle size increases from 99 to 218 nm as
the equilibrium pH increases from 3.0 to 8.0. This can be explained
by the increased nanoparticles aggregation due to lower CS solubil-
ity at higher pH values. The TEM analysis presented a homogeneous
spherical morphology with quit homogeneous and even surface with
uniform particle size distribution, Fig. 2d. The particle size diameter
obtained using the particle size analyzer (100 nm at pH 4.0) was
found to be smaller than that determined for the spherical nanopar-
ticles (120 nm) because the former was measured using swollen
nanoparticles in solution. The DSC thermogram of CS showed an en-
dothermic peak at 127 C, Fig. 2e attributed to the evaporation of wa-
ter absorbed through hydrogen bonding with CS hydroxyl groups. An
exothermic peak was observed for CS associated with its degradation
at 289 C and disappeared in the CMA thermogram indicating an in-
crease in desirable thermal stability. Moreover, the CMA thermogram
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M.A. Shaker / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 112
Fig. 1. The proposed structure of CMA nanoparticle.
shows an additional endothermic peak (H = 187.5 J/g) between 170
and 300 C, attributed to the cleavage of the strong electrostatic inter-
actions between COO and NH3 + groups responsible for the thermal
stability of CMA [17]. The TGA thermograms of CS and CMA nanopar-
ticles are shown in Fig. 2f. The degradation temperatures (Td ) for CS
and CMA were 237 2.0 and 241 2.3 C, respectively conrming
the more thermal stability of CMA than CS.
3.2. Particle size and zeta-potential analysis
Zeta-potential is an important tool for understanding the elec-
trophoretic and dispersion behaviors of CMA nanoparticles and pre-
dicting their long term stability in aqueous solution. The dependence
of zeta-potential of CMA nanoparticles on pH is shown in Fig. 2g.
The alteration of zeta-potential with pH results in changes in the sur-
face charge density of CMA nanoparticle. At low pH 1, the CMA
surface is positively charged due to protonated amine and hydroxyl
groups and this is indicated by the positive zeta-potential value. With
the increase in pH, the zeta-potential decreases because the NH3 +
groups are deprotonated and the carboxylic groups turn into carboxy-
late anions and the CMA surface becomes more negatively charged. At
pH >4.5, an increase in the net negative charge on CMA surface due
to the ionization of carboxylate groups and neutralization of amino
groups. These results indicates that the CMA nanoparticles are sen-
sitive to pH and by controlling the pH, their surface may be charged
either positively or negatively which is very important in environ-
mental applications. The zeta-potential of CMA nanoparticles reaches
the value +33.8 1.2 mV revealing a high degree of stability and in-
dicating no obvious aggregation of CMA nanoparticles.
3.3. Effect of the operating temperatures on the CMA particle size
The physical stability of CMA nanoparticles in terms of parti-
cle size was measured across a range of different operating tem-
peratures (1050 C), which is illustrated in Fig. 2h. As shown from
Fig. 2h, the particle size of CMA nanoparticles little decreased with
increasing heat treatment and this may be due to the decrease of the
surface tension with increasing temperature. It is concluded that the
CMP nanoparticles exhibited considerable thermal stability and little
affected by temperature.
3.4. Effect of pH
The solution pH in adsorption experiments is one of the most im-
portant parameters that is effective on the solution chemistry and
Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027
[m5G;June 12, 2015;11:56]
3
metal speciation and uptake capacity, adsorbent functional groups
activity and adsorption mechanism. It is directly related to the com-
petition ability of hydrogen and metal ions to the adsorbent surface
active sites [18]. Fig. 3a shows the effect of the initial solution pH (1.0
7.0) on the adsorption of Cu(II), Co(II) and Ni(II) ions onto CMA sur-
face. The maximum biosorption was observed at optimum pHs 6.0,
5.0 and 4.0 for Cu(II), Co(II) and Ni(II), respectively. At highly acidic pH
(1.0), the CMA amine and hydroxyl groups are protonated and block
the approach of metal ions to CMA binding sites and also, metal and
hydronium, H3 O+ ions complete for the same CMA binding sites and
this lowers the metal uptake [19]. At pH (4.06.0), the CMA surface
becomes more negatively charged and available for the metal pre-
dominant species in solution. The metal uptake capacity decreases at
pH (> 6.0) due to the formation of soluble hydroxylated metal com-
plexes, M(OH)+ , M2 (OH)3+ , M3 (OH)4 2+ and M4 (OH)4 4+ that compete
with the active adsorption sites [20]. Therefore, the adsorption exper-
iments could not be continued beyond pH 6.0.
3.5. Effect of adsorbent dose on adsorption
The adsorbent dosage is an important parameter that determines
the adsorbent capacity for a given initial concentration. The adsorp-
tion eciency for Cu(II), Co(II) and Ni(II) ions as a function of adsor-
bent dosage is shown in Fig. 3b. Clearly, the adsorption eciencies of
Cu(II), Co(II) and Ni(II) ions onto the CMA steeply increased (7990%)
along with increasing the adsorbent dose (2050 mg) and beyond this
optimum dose limit (50 mg) remains unchanged since the adsorption
equilibrium is reached although the number of binding sites available
for adsorption increases with increasing the biosorbent dose.
3.6. Effect of contact time
The adsorption rate is important for designing batch experiments.
Fig. 3c shows the effect of contact time (0150 min) on adsorption
of Cu(II), Co(II) and Ni(II) ions onto CMA to determine the equilib-
rium point using adsorbent dose (50 mg), initial metal concentration
(100 mg/L), and pH (6.0, 5.0 and 4.0, respectively) at 293 K. It is ob-
served that the metal removal rates at rst increase rapidly with time
(over 77% metal adsorption in the rst 70 min) where metal ions con-
tact quickly with a lot of available CMA active sites, then slowly since
these sites gradually decrease and the driving force weakens and -
nally the equilibrium is reached (100 min) and this is taken as an op-
timum contact time for further experiments.
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4 M.A. Shaker / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 112

Fig. 2. (a) FTIR spectra of CS and CMA nanoparticles, (b) size distribution of CMA nanoparticles, (c) dependence of particle size of the prepared CMA on the pH, (d) TEM micropho-
tographs of CMA nanoparticles at pH 4.0, (e) DSC curves of CS and CMA nanoparticles, (f) TGA curves of CS and CMA nanoparticles, (g) effect of solution pH on the zeta-potential of
CMA nanoparticles, (h) effect of the temperature on the average size of CMA nanoparticles.

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027
JID: JTICE
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M.A. Shaker / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 112 5

Fig. 3. Effects of different analytical parameters on the adsorption capacity of Cu(II), Ni(II) and Co(II) ions onto CMA nanoparticles: (a) effect of pH (contact time = 100 min, initial
conc. = 100 mg/L, 293 K), (b) effect of biosorbent dosage (contact time = 100 min, initial conc. = 100 mg/L, 293 K, pH 6.0, 5.0 and 4.0 for Cu(II), Co(II) and Ni(II), respectively),
(c) effect of contact time (initial conc. = 100 mg/L, 293 K, pH 6.0, 5.0 and 4.0 for Cu(II), Co(II) and Ni(II), respectively), (d) effect of initial metal concentration (contact time =
100 min, 293 K, pH 6.0, 5.0 and 4.0 for Cu(II), Co(II) and Ni(II), respectively).

3.7. Effect of initial metal ions concentration
Fig. 3d shows the effect of initial metal concentration (10, 20, 50,
70, 100, 200 mg/L) on the metal uptake at optimum experimental
conditions. The results indicate that the percentage of metal removal
increases with increasing initial concentrations till certain maximum
limit and them remains unaffected. The removal eciency of Cu(II),
Ni(II) and Co(II) were 90%, 86%, and 80%, respectively. The highest
sorption eciency of Ni(II) ion was ascribed to the excellent an-
ity of CMA to Ni(II) leading to more occupation of active sites and
increased interaction between Ni(II) and CMA nanoparticles. The ap-
propriate metal ion concentration for adsorption experiments is se-
lected to be 100 mg/L.
3.8. Adsorption equilibrium isotherm
The experimental equilibrium data for the adsorption of Cu(II),
Co(II) and Ni(II) onto CMA at the optimum conditions were applied
to Langmuir [21] and Freundlich [22] models, Fig. 4a. It is clear that
Langmuir model accurately represents the data more than Freundlich
model, Fig. 4a. Langmuir model is the most often used isotherm for
the adsorption of a solute from a liquid solution and assumes uniform
monolayer formation of adsorbate molecules onto adsorbent surface,
negligible interacted adsorbed molecules and equienergy adsorption
sites. Moreover, once the sorbate occupies a site, no further sorption
can take place at this site. The Langmuir adsorption isotherms for
Cu(II), Co(II) and Ni(II) at optimum conditions are shown in Fig. 4b.
The nonlinear form of Langmuir isotherm is given by Eq. (3) and Fig.
4b [21].
K ce
qe = (3)
1 + KCe
where qe (mg/g) and ce (mg/L) have the same denitions as in Eq.
(1), K (L/mg) is the conditional adsorption equilibrium constant and
(mg/g) is the stoichiometric adsorption site capacity. The linearized
form of Langmuir isotherm is represented by Eq. (4).
1 1 1
= + (4)
qe K Ce

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027
JID: JTICE
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6 M.A. Shaker / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 112

Fig. 4. Adsorption data for Cu(II), Co(II) and Ni(II) onto CMA at optimum pH values and 293 K: (a) theoretical and experimental data at optimum conditions, (b) Langmuir isotherms,
(c) plots of 1/qi vs. 1/ce , (d) plots of linear forms of Freundlich model, (e) plots of ln Ki vs. 1/T for Langmuir model data, (f) correlation of enthalpy and entropy changes (data from
Table 1) for metal adsorption by solid CMA.

The applicability of Langmuir isotherm to the experimental data can
be tested from linearity of 1/qe vs. 1/ce plots, Fig. 4c. These plots in
Fig. 4c can be a linear segment representing one adsorption step (as in
case of Co(II) ions) or two linear segments with distinctive slopes and
excellent R2 values (as in case of Cu(II) and Ni(II) ions) representing
two adsorption steps. Each adsorption step represents an adsorption
site occupation [510]. The values of K and for each adsorption site
can be calculated from the slope and intercept of the corresponding
linear segments, Table 1. It is concluded that three stoichiometric ad-
sorption sites, i (i = A, B or C) on CMA surface can be recognized with

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027
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M.A. Shaker / Journal of the Taiwan Institute of Chemical Engineers 000 (2015) 112 7

variable capacities i , Table 1. The values of i vary little with tem-

0.94
0.93
0.91
perature and are averaged to be 76 3, 119 5 and 222 4 mg/g,

R2

-
-
-
-
-
-
respectively. When the calculated vi for adsorption step in one of the

(mg/g(L/mg)1/n )
investigated Cu(II), Co(II) and Ni(II) metals approaches one of those

Freundlich model
vi values, this means that this given metal ion bind selectively to the
corresponding site, i. The trend in i to increase as the binding goes
from step A to B to C is seen in all of these systems. Fig. 4c shows

3.0 4.7
2.7 4.9
2.7 5.1
K

-
-
-
-
-
-
that Cu(II) has two adsorption steps, A and B (two linear segments,
R2 1) with vi (76 and 119 mg/g, respectively), Co(II) has only one ad-

-
-
-
-
-
-
sorption step, C (one linear segment, R2 1) with vi (222 mg/g) and

(kJ/mol) (J/mol.K) (kJ/mol)

33.2

29.7

36.9
31.3
28.1

35.1
nally, Ni(II) cations prefer to bind in two sequential steps to sites B

G0
and C on CMA surface with vi (119 and 222 mg/g, respectively). The

-
cumulative site capacities for Cu(II), Co(II) and Ni(II) were 195 (sites

129.9
119.7

129.9
119.7

129.9
119.7
A, B), 220 (site C) and 340 (sites B, C) mg/g, respectively follows the

S0
order of the hydrated ionic radii (Ni > Co > Cu). Also, the suitability

-
of Langmuir model for an adsorption system can be conrmed using

H0

21.4
18.4

21.4
18.4

21.4
18.4
another linear form of Langmuir isotherm, Eq. (5) and plots of ce /qe

-
vs. ce , can be made.

0.69

0.79

0.81
0.86
0.73
0.57
RL

-
Ce Ce 1
= + (5)

0.94

0.98
0.99
0.95

0.99
0.97
qe K

R2

-
(L/mg)

4 0.030
5 0.039

5 0.086
The values of equilibrium constants, Ki are seen to decrease from

4 0.076

4 0.166
5 0.178
KC
step A to B to C, Table 1. The value of KC for Ni(II) ions is larger than

-
KC for Co(II) ions and the value of KB for Ni(II) ions is larger than KB

(kJ/mol) (J/mol.K) (kJ/mol) (mg/g)

Site C
for Cu(II) ions and this follows the order in metals electronegativity,

220

220
219

220
219

219
C
hydrated ionic radii, metals electron conguration and ligand eld

-
stabilization energies, Table 1 [23]. The linear regression is frequently

11.2
31.7

11.9
33.4

12.5
30.1
used to determine the most tted isotherm model and the method

G0
of least squares can be used to nd the model parameters. It was

-
found that the Langmuir model parameters for the investigated sys-

79.3

79.3

66.3
122.0

122.0

122.0
tems were statistically signicant at 95% condence levels (R2 1.0).

S0
A dimensionless separation factor, RL . Eq. (6) may be used to ex-

-
press the essential characteristics of Langmuir isotherm [511,24].
The RL value indicates the adsorption nature to be unfavourable (RL > H0

19.9

7.3
19.9

7.3
19.9

8.2
1), linear (RL = 1), favourable (0 < RL < 1) and irreversible (RL = 0).

-
0.69

0.81

0.84

0.88
0.77
0.73
The values of RL , Table 1 were (0.420.88) for initial concentrations
RL

-
(5250 mg/L) indicating favorable adsorption processes.

0.98

0.98
0.96

0.99

0.99
0.97
R2

-
1
RL =
(L/mg)

(6)
2 0.206
5 0.054

3 0.269
5 0.235
3 0.132
3 0.143

1 + Kc0
KB

-
Freundlich adsorption model assumes different adsorption sites with
Adsorption equilibrium and thermodynamic parameters for the investigated systems.

(kJ/mol) (J/mol.K) (kJ/mol) (mg/g)

Site B

variable energies on irregular solid surface and intractable adsorbed

119

121
121

122
124

120
B

species within a specic concentration range, Eq. (7) [22].

-

qe = KF ce1/n
16.3

17.2

18.1

(7)
G0

-
-

-
-

-
-

where qe (mg/g) and ce (mg/L) have the same denitions as in

Eq. (1). The constant KF is a function of adsorption energy and
90.6

90.6

90.6
S0

temperature and measures the adsorptive capacity while the con-

-
-

-
-

-
-

stant n determines the intensity of adsorption (adsorbentadsorbate

bond strength) and nature of adsorption. The value n > 1 describes
H0

0.98 0.42 11.5

0.99 0.53 10.3

0.97 0.61 10.3

favorable adsorption, n = 1 characterizes linear adsorption and

-
-

-
-

-
-

n < 1 describes unfavorable adsorption situations. The linear form of

RL

-
-

-
-

-
-

Freundlich isotherm is shown in Eq. (8).

R2

-
-

-
-

-
-

1
log qe = log ce + log KF (8)
T (K) Cation Langmuir model

(L/mg)

n
0.223

0.367

0.491
KA

-
-

-
-

-
-

The slope and intercept of linear plot of log qe vs. log ce gives the ad-
(mg/g)

76 3

78 4

74 2
Site A

sorption parameters, Fig. 4d and Table 1. The derived values of KF and

A

n were [4.75.1 mg/g (L/mg)1/n ] and [2.73.0 mg/g], respectively. The

-
-

-
-

-
-

values of 1/n (<1) are indicative of unfavorable adsorption. Also, the

Cu(II)

Cu(II)

Cu(II)
Co(II)

Co(II)

Co(II)
Ni(II)

Ni(II)

Ni(II)

low KF values indicated low adsorption capacity and the lower values
of R2 (0.910.94) compared to Langmuir reveal that Freundlich model
Table 1

293

323
313

is not suitable approach for describing the adsorption behavior in this

study.

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3.9. Adsorption thermodynamics

The vant Hoff equation, Eq. (9) used to evaluate the variation of
equilibrium constant with temperature determines the thermody-
namic parameters for adsorption processes.

Sio Hio
ln Ki = (9)
R RT
where Ki (L/mol) is the conditional equilibrium constant,
Sio (J/mol. K) is the standard entropy change, Hio (kJ/mol) is
the standard enthalpy change for step i, T (K) is the absolute tem-
perature and R (8.314 J/mol K) is the ideal gas constant. The values Hence the pH will decrease when metal concentration increased.
of Hio and Sio can be determined from the slopes and intercepts The high calculated values, Table 1 for the investigated Cu(II), Co(II)
of linear regression of ln Ki vs. 1/T, Fig. 4e. The standard Gibbs free and Ni(II) systems indicated high CMA anity to adsorb these metal
energy change, Goi (kJ/mol) for step i at temperature, T can be ions.
calculated from Eq. (10).
3.11. Adsorption kinetics
Goi = Hio T Sio (10)
Generally the proles of metal ion uptake versus time always be-
The adsorption experiments of Cu(II), Co(II) and Ni(II) onto CMA gin with a rapid phase followed by a relatively slow phase [27] and
were carried out at 293, 303 and 313 K. The H, S and G for this trend can be observed in Fig. 3c. Elucidation of the adsorption ki-
these adsorption processes and each characterized site are recorded netic parameters, mechanisms and adsorbent characteristics is nec-
in Table 1 and were 11.5 kJ/mol, 90.6 J/K and 16.3 kJ/mol, respec- essary for larger scale applications. Adsorption could be dependent
tively for step A and 19.9 kJ/mol, 122.0 J/K and 30.1 kJ/mol, re- on and controlled by different mechanisms such as diffusion con-
spectively for step B in Cu(II) system, 21.4 kJ/mol, 129.9 J/K and trol, mass transfer, chemical reactions and particle diffusion. Four ki-
33.2 kJ/mol, respectively for step C in Co(II) system and 7.3 kJ/mol, netic models, the pseudo-rst order, pseudo-second order, modied
79.3 J/K and 11.2 kJ/mol, respectively for step B and 18.5 kJ/mol, Ritchies second order and intraparticle diffusion have been used to
119.7 J/K and 28.1 kJ/mol, respectively for step C in Ni(II) system. describe the kinetics and the rate limiting step for the present in-
The positive H values indicate endothermic adsorption character, vestigated systems at different temperatures (293313 K). The simple
which is evidenced by increasing Ki with temperature, Table 1. The pseudo-rst order kinetic model of Lagergren is given as Eqs. (11) and
endothermicity is explained as the metal ion has to displace more (12) [28].
than one water molecule for its adsorption and formation of coordi-
nation complex with CMA. Meanwhile, the positive S values iden- dqt
= k1 (qe qt ) (11)
tied the increasing trend in randomness at solidsolute interface dt
during adsorption caused by this water release [25]. The negative
G values indicated feasible and spontaneous adsorption processes. ln(qe qt ) = ln qe k1 t (12)
However, the negative G values for all metal ions increased with
The pseudo-second order kinetic model can be expressed by Eqs.
temperature, indicating more favorable adsorption at higher temper-
(13) and (14) and the initial adsorbent rate h (mg/g/min) can be de-
atures as CMA nanoparticles were well dispersed at high tempera-
termined from k2 and qe values using Eq. (15) [29].
ture and aggregated at low temperature. Therefore, temperature is
one of the controllable factors in endothermic metal adsorption pro- dqt
= k2 (qe qt )2 (13)
cesses. The same behavior at all three temperatures supports use of dt
Langmuir model to describe these investigated adsorption systems.
The linear plot of Hi vs. Si (i = A, B, or C), Fig. 4f shows that t 1 1
= + t (14)
Hi and Si are correlated for different metals adsorbed onto dif- qt k2 q2e qe
ferent sites on the solid CMA surface. Its linearity is a test of the
appropriateness of Langmuir model and strengthens what was pre- h = k2 q2e (15)
viously concluded. The intercept of this straight line represents the
The modied Ritchies-second order kinetic model is given by Eq.
average G (16.07 kJ/mol) indicating favorable but mildly exer-
(16) [30].
gonic processes and that CMA acts as free energy buffer during ad-
sorbing metals. The slope of the line is the absolute temperature 1 1 1
= + (16)
(298.4 K). qt kR qe t qe
Finally, the intraparticle diffusion model can be described by Eq.
(17) [31].
3.10. Adsorption mechanism
qt = ki t 1/2 (17)
The binding mechanisms of metal ions onto chitosan-based nano-
materials are not yet fully understood and are now assumed to where k1 (/min) is the rate constant of pseudo-rst-order adsorp-
tion, qe and qt (mg/g) denotes the amount of metal ions adsorbed
occur through several single or mixed interactions: chelation or co-
at equilibrium and at time, t (min), respectively, k2 (g/mg/min) is
ordination, electrostatic attraction or ion exchange and formation of
ion pair [26] depending on the metal ion, its chemistry, pH and adsor- the pseudo-second-order rate constant of adsorption at equilibrium,
kR (/min) is the rate constant of the modied Ritchies-second-order
bent chemical and physical nature. The complexation between lone
kinetic model and ki ((mg/g ) min1/2 )) is the intraparticle diffusion
electron pairs of CMA soft base ligands (amino group and/or hydroxyl
rate constant. The validity of the adsorption reaction order is based
groups) and the metal void orbitals would be formed. MetalCMA
on three criteria that are the regression coecients, predicted qe val-
complex may be accompanied either by proton release or by hydrox-
ues and normalized standard deviation, Fig. 5ad [27].
ide ion xation as follows:

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
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Fig. 5. The experimental conditions are: initial metal concentration of 100 mg/L, optimum pH for each metal ion, 50 mg CMA adsorbent dose, contact time (5300 min), shaking
rate 200 rpm and different temperatures (a) the plot of Lagergren pseudo-rst order kinetic equation, (b) the plot of pseudo-second order kinetic equation, (c) the plot of modied
Ritchies-second order kinetic equation, (d) the plot of intraparticle diffusion kinetic equation, (e) the effect of temperature (293, 303 and 313 K) on the pseudo-second order rate
constant.

To quantitatively compare the kinetic model applicability, a nor-

   1/2
(qe,exp qe,cal )
malized standard deviation (q) representing the agreement be-  q (% ) = 100 sum / (n 1 ) (18)
qe,exp
tween the experimental and predicted data points and providing a
numerical measure to interpret the goodness of t is given by Eq. (18)
where n is the number of data points (n = 7), qe ,exp and qe,cal are the
[32].
experimental and calculated adsorbent capacities, respectively. The

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
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Table 2
Kinetic parameters of the four investigated adsorption models.

Cu(II) Co(II) Ni(II)

293 K 303 K 313 K 293 K 303 K 313 K 293 K 303 K 313 K

qe,exp (mg/g) 181.3 180.5 183.1 212.3 214.5 210.9 276.3 277.1 275.6
Pseudo-rst order k1 x 103 (L/min) 3.5 3.8 4.1 4.2 4.7 5.2 5.3 6.1 7.9
qe,cal (mg/g) 158.6 158.8 159.3 187.3 190.3 187.6 247.2 249.3 247.9
R2 0.92 0.90 0.91 0.91 0.91 0.93 0.93 0.93 0.92
q (%) 5.1 4.9 5.3 4.8 4.6 4.5 4.3 4.1 4.0
Pseudo-second order k2 x 103 (g/mg/min) 0.09 1.5 2.7 1.5 3.1 4.7 18.1 31.0 56.4
qe,cal (mg/g) 177.2 176.5 178.9 207.7 209.9 206.4 271.5 272.1 270.6
R2 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
h (mg/g/min) 1.3 1.1 1.0 1.2 1.3 1.2 0.9 0.9 0.8
q (%) 0.92 0.91 0.94 0.88 0.87 0.88 0.71 0.73 0.74
Ea (kJ/mol) 45.8 47.7 49.3
Modied Ritchies-second order kR x 102 (L/min) 6.6 8.1 9.4 7.5 8.9 11.0 8.5 10.0 12.5
qe,cal (mg/g) 173.9 173.0 175.6 204.2 206.2 202.7 266.4 267.0 265.6
R2 0.97 0.98 0.97 0.98 0.98 0.97 0.99 0.97 0.98
q (%) 1.67 1.69 1.68 1.56 1.57 1.59 1.46 1.49 1.48
Intraparticle diffusion ki x 101 (L/min) 9.8 10.7 12.3 11.2 13.1 15.3 14.6 16.4 18.9
qe,cal (mg/g) 140.9 140.7 143.2 168.6 164.0 165.9 221.5 222.8 220.2
R2 0.90 0.91 0.91 0.92 0.93 0.92 0.90 0.91 0.91
q (%) 9.1 9.0 8.9 8.4 9.6 8.7 8.1 8.0 8.2

Table 3
Maximum adsorption capacity of various chitosan-based materials for Cu(II), Co(II) and Ni(II) ions.

Chitosan-based material qmax (mg/g) Reference

Cu(II) Co(II) Ni(II)

Chitosan/cotton bers (via Schiff base bond) 24.78 7.63 [36]

Chitosan/magnetite 52.55 [37]
Chitosan/cellulose 26.5 13.2 [38]
Chitosan/perlite 196.07 114.94 [39]
Chitosan/ceramic alumina 86.20 78.10 [40]
Chitosan/alginate 67.66 [41]
Chitosan/calcium alginate 222.20 [42]
Chitosan/silica 254.30 [42]
Chitosan/PVC 87.90 120.50 [43]
Chitosan/clinoptilolite 719.39 467.90 247.03 [44]
Montmorillonite modied with chitosan 150.00 [45]
EDTA-modied chitosan 79.70 [46]
Glycine grafted chitosan 165.91 82.90 [47]
Chloroacetic grafted chitosan 175.12 59.1 [47]
CMA 195 220 340 Present work

values of the kinetic parameters, correlation coecients and normal-
ized standard deviations obtained from different kinetic models are
all listed in Table 2.
Although the plots of the pseudo-rst order kinetic model and
intraparticle diffusion model were linear, the qe,cal values were not
in agreement with qe,exp , indicating a poor t. Moreover, these
models could not be perfectly applicable over the initial stage of
the adsorption processes. It is clear that Fig. 5b representing the
pseudo-second-order kinetic model shows a good agreement to data.
The pseudo-second order kinetic model could predict the kinetic be-
havior over the whole contact time. Also, for the pseudo-second-
order kinetic model the R2 values are extremely high (1.0) while
q (%) values are low (0.710.94), followed by those of modied
Ritchies-second order kinetic model (R2 = 0.970.99; q (%) = 1.46
1.69; Fig. 5c), those of pseudo-rst-order kinetic model (R2 = 0.90
0.93; q (%) = 4.05.3; Fig. 5a) and nally those of intraparticle dif-
fusion model (R2 = 0.900.93; q (%) = 8.09.6; Fig. 5d), respectively,
Table 2. Meanwhile, the qe,cal values estimated from pseudo-second-
order kinetic model agree perfectly with the qe,exp values indicating
the best tting to pseudo-second order model (followed by modied
Ritchies-second-order kinetic model) and the chemisorption charac-
teristics [33].
3.12. Effect of temperature on adsorption kinetics
The Arrhenius type relationship is expressed by Eq. (19) [34].
Ea
ln k2 = ln k0 (19)
RT
where k2 is the pseudo-second-order rate constant (g/mg/min), k0 is
the independent temperature factor (g/mg/min), R is the gas constant
(8.314 J/mol/K), T is the solution temperature (K) and Ea is the activa-
tion energy (J). The magnitude of Ea explains the type of sorption. The
values of the pseudo-second-order rate constant, k2 for initial metal
concentrations (100 mg/L) were found to increase with temperature
for all studied system, Fig. 5e and Table 2 due to accelerated metal ion
transport from bulk to CMA surface resulting in more rapid metal up-
take. The magnitude of Ea determines the type of sorption where Ea
28 kJ/mol indicates physical adsorption (rapid and ease equilibrium)
while Ea > 43 kJ/mol indicates chemical adsorption. The calculated
Ea values for the studied systems were 45.8, 47.7 and 49.3 kJ/mol
for Cu(II)CMA, Co(II)CMA and Ni(II)CMA systems, respectively
indicating both diffusion-controlled adsorption and chemisorption
situation [35]. Moreover, increasing qe also indicated the endother-
mic property of adsorption. For the adsorption system where the

Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
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pseudo-second-order model ts adsorption kinetics, the chemical in-
teraction is important in the rate-controlling step, where tempera-
ture is highly signicant parameter.
3.13. Desorption of CMA
The stability and reusability of an adsorbent during adsorption/
desorption cycles are important factors in designing large-scale ap-
plications from the environmental and economic points of view. The
metals adsorbed on the surface of biosorbents can be recovered by
desorption with adequate eluents. Though acids such as HCl and
HNO3 are excellent elution agents to desorb metals they decrease the
metal adsorption ability of the regenerated biosorbent due to hydrol-
ysis of the polysaccharides on the chitosan surface. Therefore, in this
work EDTA was preferably selected to be used as a desorbent. A so-
lution of EDTA (0.01 M) was used as an elution agent for desorbing
cobalt, nickel and copper ions from the used CMA sorbent for three
successive adsorption-regeneration cycles, where 85.4, 86.9 and
88.9% desorption eciencies for Co(II), Ni(II) and Cu(II), respectively
were achieved. There was 2% reduction of qe of metal ions desorbed
from the rst to second cycle but the amount of desorption have lit-
tle change after three cycles. The percentages of the desorption metal
ions could be improved by increasing the concentration of EDTA.
3.14. Comparison of biosorption capacity of CMA with reported
adsorbents
A comparison of the maximum Cu(II), Co(II) and Ni(II) adsorption
capacity, qmax (mg/g) on CMA and some other chitosan and chitosan-
based materials as adsorbents reported in the literatures [3647] are
shown in Table 3. In the present work, the qmax of CMA were 195 (sites
A and B), 220 (site C), and 340 (sites B and C) mg/g, respectively which
were comparable and indicated that CMA solid phase had a high sorp-
tion capacity and excellent performance towards Cu(II), Co(II) and
Ni(II) attributed to its high specic area, widely distributed pores, and
plenty of powerful chelating groups.
4. Conclusions
In this work, regular shaped CMA nanospheres (100120 nm) pre-
pared by chemical polymerization reaction of CS with MA were used
as highly ecient metal ion chelator and were benecial from their
cross-linked, porous morphology and plenty of chelating groups. The
qmax of CMA was much higher than those of reported chitosan-based
materials. Meanwhile, qe was highly dependent on pH value, CMA
dose, temperature, initial ionic concentration and time because the
adsorption was favourable, endothermic and of chemical nature and
correlated to Langmuir isotherm and the pseudo-second order ki-
netic model. Different binding sites are distinguished on CMA surface
that selectively binds to metal ions in sequential adsorption steps.
The aforementioned results suggest that CMA nanoparticles are ef-
cient for selective elimination of Cu(II), Co(II) and Pb(II) pollution
from wastewater.
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Please cite this article as: M.A. Shaker, Adsorption of Co(II), Ni(II) and Cu(II) ions onto chitosan-modied poly(methacrylate)
nanoparticles: Dynamics, equilibrium and thermodynamics studies, Journal of the Taiwan Institute of Chemical Engineers (2015),
http://dx.doi.org/10.1016/j.jtice.2015.05.027