Reactive & Functional Polymers 75 (2014) 1–8

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Reactive & Functional Polymers

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

Preparation of poly(acrylic acid)/starch hydrogel and its application

for cadmium ion removal from aqueous solutions
E.S. Abdel-Halim ⇑, Salem S. Al-Deyab
Petrochemical Research Chair, Chemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia

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

Article history: In this paper, potassium bromate/thiourea dioxide redox system was used to initiate the graft copolymer-
Received 26 September 2013 ization reaction of acrylic acid onto maize starch. The so obtained polyacrylic acid/starch graft copolymer
Received in revised form 18 November 2013 was crosslinked by further treatment with alkaline epichlorohydrin to get three dimensional hydrogel.
Accepted 7 December 2013
This crosslinked hydrogel was used for the removal of the heavy element, Cd2+ from its aqueous solution
Available online 12 December 2013
by adsorption. All factors which are expected to affect the adsorption process, like adsorbent concentra-
tion, immersion time, graft yield of the adsorbent, Cd2+ concentration and adsorption temperature were
Keywords:
extensively studied and reported in the text. The study and investigations demonstrated that the
Starch
Hydrogel
adsorption efficiency is affected by the adsorbent graft yield and the adsorption medium temperature.
Adsorption In addition, on fitting the data obtained from the adsorption process, it was found that the adsorption
Cadmium ion obeys both Langmuir and Freundlich adsorption isotherms but the Langmuir isotherm shows better
mathematical fitting for the equilibrium data than does Freundlich model, based on the higher R2 value
for the Langmuir isotherm.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Many natural polymers, especially those coming from cultiva-
tion wastes, have been extensively reported as efficient adsorbents
for different heavy metal cations. Fibers, bark and leaves of many
agricultural products as well as other industrial wastes and indus-
trial byproducts, like sawdust, jute processing wastes and many
other processing wastes are used for heavy metal ions removal
from wastewater. For metal ion removal, one can use these indus-
trial and/or agricultural wastes and byproducts without any
chemical modification, as such or these agricultural wastes and
byproducts can be subjected to further functionalization to intro-
duce new functional groups or increase the content of originally
found functional groups. This functionalization or chemical modi-
fication can be achieved through different chemical techniques
like, for example grafting reactions onto the cellulosic component
of these wastes and byproducts to meet the required performance
requirements of their end-use as adsorbents for heavy metal
removal. Recent research in utilization of agricultural and
industrial wastes and byproducts in removal of heavy metal
cations from wastewater include the use of apple wastes [1],
eggshell [2], peanut hull [3], pectin-rich fruit wastes [4], rice husk
[5], sawdust [6] pulp and paper industrial wastes [7,8]. Adsorption
⇑ Corresponding author. Tel.: +966 566186116.
E-mail address: essamya@yahoo.com (E.S. Abdel-Halim).
of the metal ions by any of the carbohydrate polymers takes place
by the attraction mechanism, depending on the difference in
charge between the positively charged metal cations and the
negatively charged active sites distributed everywhere along the
backbone of any carbohydrate polymer, and these active sites
govern the whole uptake of the metal cations by the carbohydrate
polymers. The most widely abundant function groups present in
the structure of any carbohydrate polymer are hydroxyl groups
and carbonyl groups but although these hydroxyl and carbonyl
groups are present in great abundance, they are not effective sites
for attracting and removing the metal cations. Functional groups
like carboxyl groups were found to have a very governing role in
removing heavy metal cations, that they bind to the heavy metals
through salt formation. X-ray spectroscopy was used to investigate
the ligands of chromium and nickel cations in some biomass and
spectral data confirmed the binding between these metals and
the carboxyl groups spread along the biomass structure [9].
Adsorption of cadmium ions by juniper fiber was reported and
when FTIR spectroscopy analysis was carried out on the fibers
loaded with the metal cations, strong peak characteristic for the
carboxylate ion was found in the FTIR spectra [10]. Moreover,
DRIFT spectroscopy was used to study the mechanism of cadmium
ion removal by both juniper bark and juniper wood. It was
concluded from this study that the uptake of cadmium ions by
the juniper bark is higher, compared to the cadmium ions uptake
by the juniper wood. This difference in metal ion uptake in both
cases was found to be due to clear difference in the amounts of

1381-5148/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.reactfunctpolym.2013.12.003
2 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8
carboxyl groups on the surface of each material [10]. Another stud-
ies [11–13] reported the contribution of the ion exchange mecha-
nism, beside adsorption mechanism in the overall metal uptake by
the carbohydrate polymers containing carboxyl groups in their
structures. The efficiency of the native carbohydrate polymer, in
removing heavy metals from aqueous solutions is not high com-
pared to the pretreated or chemically modified carbohydrate poly-
mers. This is due to the low accessibility of carbohydrate polymers
in the native form which does not allow the ionic species to mi-
grate to the bulk of the polymer. For example, although native cel-
lulose and native starch contain large number of hydroxyl groups,
these hydroxyl groups are not available to undergo coordination
with heavy metals, when in contact with them in aqueous solu-
tions, due to the high crystallinity of the native cellulose and the
amylose constituent of native starch. To overcome this problem
and improve the metal uptake in the bulk of adsorbents based on
carbohydrate polymers, many authors attempted to modify these
polymers by pretreatment and functionalization of such carbohy-
drate polymer. The chemical modification and surface functionali-
zation could improve the adsorption capacity and increase the
heavy metal uptake by different carbohydrate polymers [14–19].
Mohan and Sreelakshmi reported the utilization of rice husk mod-
ified phosphates for the effective removal of heavy metal ions from
their aqueous solutions [20]. Enhancement of Douglas fir bark-
binding capacities to lead ions of after chemical modification of
the former was reported by Astier et al. [21]. Cox et al. could con-
vert flax shive by-product to carbon by chemical activation
through treatment with hot sulfuric acid [22]. This activated car-
bon was used by Cox et al. for separation of heavy metals like gold,
silver, palladium and platinum. They found that the sorption pro-
cess for all metal ions obey Langmuir isotherm and that the sorp-
tion process takes place by ion exchange mechanism through
reaction of the metal cations with the functional groups present
in the activated carbon [22].
Different chemical modifications of carbohydrate are generally
carried out either to improve the performance properties of these
polymer to be suitable for use in certain applications, like for
example clothing [23–25] or to introduce certain chemical moiety
to achieve certain property, like for example strong reduction
potential [26]. Grafting is also a very important route for chemical
modification of carbohydrates, that for example grafting of mono-
mers bearing functional groups like carboxyl group, amino group
or sulfonic acid group, onto carbohydrate polymers, followed by
network formation through crosslinking, which improves the
performance of such natural polymers for their use in metal ion
removal [27–32]. In these three dimensional hydrogels, the func-
tional groups grafted onto the polysaccharide backbone operate
in metal ion removal by either adsorption mechanism or ion
exchange mechanism. Chauhan et al. [33] reported the use of
cellulose-based hydrogel for adsorption of iron (II) copper (II)
and chromium (VI) from wastewater. They found the metal
removal capacities to be enhanced to good extent by partially
saponifiying the attached amide group to carboxylic group. In the
present article, we report the utilization of a novel hydrogel based
on starch, modified through graft copolymerization with polyacry-
lic acid for the removal of cadmium ions from wastewater. Grafting
with acrylic acid is carried out to introduce high content of
carboxyl groups to the starch backbone. Then the graft copolymer
is crosslinked to hydrogel that will be used for the adsorption of
heavy metals from aqueous solutions. The hydrogels is character-
ized by measuring its carboxyl content, while the hydrogel capac-
ity to remove heavy metals from their aqueous solutions is
evaluated by measuring the metal ion concentration in the
aqueous solution before and after adsorption by means of atomic
absorption.
2. Experimental
2.1. Materials
Starch maize and acrylic acid were purchased from Acros. Other
chemicals like cadmium nitrate, potassium iodide, sulphuric acid,
thiourea dioxide (TUD), potassium bromate, potassium bromide
and sodium thiosulphate were all laboratory grade reagents.
2.2. Preparation of poly(acrylic acid)/starch graft copolymer
Starch in water slurry was mechanically stirred in a thermo-
static water bath until the predetermined polymerization temper-
ature was attained. After the desired polymerization temperature
was attained, calculated amount of the monomer acrylic acid
(AA) is added and stirring is continued in the thermostatic water
bath until the predetermined polymerization temperature was
attained again. Aqueous solutions of the initiation system compo-
nents, potassium bromate (PB) and thiourea dioxide (TUD), were
added, respectively to the polymerization medium, such that the
final material to liquor ratio (M/L) (solid starch: total polymeriza-
tion liquor) is 1:5 and the polymerization reaction was allowed to
proceed under continuous stirring for the predetermined reaction
duration [34]. Poly(acrylic acid)/starch graft copolymer (PASGC)
was removed from homo polyacrylic acid by precipitating the
former in ethanol, filtering and washing thoroughly with hot water
for several times and then with cold water and finally dried at 50 °C
overnight. The graft yield of PASGC was calculated according to the
following equation:
W2  W1
%G:Y: ¼  100
W1
where W1 is the absolute dry weight of the starch sample before
grafting and W2 is the absolute dry weight of PASGS sample.
2.3. Synthesis of hydrogels
Ten grams sample of finely grinded PASGC was treated with
100 mL of sodium hydroxide solution aqueous solution (0.1 N)
and the system is stirred mechanically until PASGC is completely
dissolved in the alkaline solution. At this moment, different
amounts of epichlorohydrin (ECH) (1–10 g) were added drop wise
to the graft copolymer solution under continuous and vigorous
stirring conditions for 60 min to prepare hydrogel samples having
different degrees of crosslinking. After complete crosslinking, the
graft copolymer is converted to paste. The paste is separated from
the crosslinking medium, dried in an air oven at 50 °C overnight
and then cured at different temperatures ranging from 120 °C to
170 °C for 2 min and finally again grinded to fine particles [35].
2.3.1. Swelling capacity measurement
Swelling behavior of the hydrogel was studied in water at fixed
temperature of 30 °C, as a function of curing temperature and
extent of crosslinking. To study the effect of curing temperature
on the swelling, dry hydrogel samples (1 g each), crosslinked
using 5 g ECH and prepared using different curing temperatures
(120–170 °C) were immersed for 240 min in distilled water at
30 °C. To study the effect of extent of crosslinking on the swelling
capacity, dry hydrogel samples, 1 g each (ECH used in crosslinking
ranges from 1 g to 10 g) were immersed in distilled water at 30 °C
for 240 min. After the immersion time is vanished, the swollen
hydrogel samples were wiped off carefully without any pressure
with tissue paper in order to remove the excess water from the
hydrogel surface and then weighed immediately. The swelling
capacity (SC) (g water/g hydrogel) is given by the equation [36]:
 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8 3

SC ¼ M 2  M 1

where M1 is the mass of the dry hydrogel before immersion and M2

is the mass of the swollen hydrogel.

2.3.2. Mechanical properties measurement

In order to show the effect of crosslinking extent on the
mechanical properties of the hydrogel, hydrogel samples cross-
linked with different amounts of ECH (1–10 g) were prepared
and casted in the form of films. The tensile strength was measured
at a strain rate of 5 mm/min (ASTM D-1822L). The tensile strength
for each film was measured in triplicate and the mean value was
recorded.

2.3.3. FTIR spectroscopic analysis Scheme 1. Cd2+ ion desorption and hydrogel regeneration.
FTIR spectra were recorded on a Perkin Elmer 1B16x 11-FTIR
Spectrophotometer by use of potassium bromide disk technique.
The samples were grinded with potassium bromide and pressed 3. Results and discussions
using pressure of 400 kg/cm for 10 min. The measurements were
carried out in the range 4000–400 cm1. 3.1. Hydrogel properties

3.1.1. Effect of crosslinking extent on the swelling capacity of the

2.4. Adsorption studies hydrogel
Fig. 1 illustrates the effect crosslinking extent, expressed in
1.5 g of cadmium nitrate was dissolved in certain volume of dis- terms of epichlorohydrin concentration, during the crosslinking
tilled water, then transferred quantitatively to 1 l volumetric flask step, on the swelling capacity of the prepared hydrogel. It is clear
and the solution is diluted with distilled water to the mark to yield from the figure that each increase in epichlorohydrin concentra-
a stock solution containing 1500 mg cadmium ion per liter. This tion, until 5 g is accompanied by an increase in the swelling capac-
stock solution was used to prepare standard solutions of Cd2+ hav- ity of the hydrogel. The improvement in the swelling capacity by
ing concentrations ranging 50–1000 mg/l through proper dilution increasing ECH concentration is quite logic, as it enhances the net-
of definite volumes from this stock solution. A 100 ml sample of work structure of the hydrogel, through increase in the number of
each Cd2+ standard solution was transferred to 150 ml Erlenmeyer crosslinks. Further increase in the ECH concentration above 5 g was
flask, in which definite weight of the adsorbent (hydrogel) was pre- found to be accompanied by continuous decrease in the swelling
viously placed. The adsorbent was allowed to be immersed in the capacity of the hydrogel. This could be attributed to the higher
Cd2+ standard solution for predetermined durations and at the crosslinking density in the hydrogel network structure as the con-
end of this duration, the adsorbent hydrogel was removed from centration of ECH increases above certain limit. This high crosslink-
the Cd2+ ion solutions and the residual Cd2+ was immediately esti- ing density restricts the penetration of more water molecules into
mated in the solution by means of atomic absorption. Similar blank the network structure of the hydrogel.
experiments (without adding adsorbent to the metal ion solution)
were carried out in parallel manner and the Cd2+ was immediately
3.1.2. Effect of curing temperature on the swelling capacity of the
estimated in the solution by means of atomic absorption. The
hydrogel
amount of Cd2+ ions removed by adsorption onto the hydrogel
Fig. 2 shows the effect of curing temperature, during the hydro-
was mathematically calculated from the difference in Cd2+ concen-
gel preparation on the hydrogel swelling capacity. It is clear from
tration in the blank metal ion solution and Cd2+ concentration in
the figure that, raising the curing temperature from 120 °C to
the exhausted metal ion solution.
150 °C is accompanied by noticeable improvement in the swelling
capacity of the hydrogel and this could be interpreted in terms of
2.5. Desorption and regeneration studies enhancement in the crosslinking reaction by raising the curing
temperature. Further increase in the curing temperature above
0.3 g of the hydrogel adsorbent was agitated in 200 ml of Cd2+ 150 °C was found to have no effect on improving the swelling
solution of concentration 1000 mg/l. The agitation was carried capacity of the hydrogel.
out for 180 min at 30 °C. The adsorbent hydrogel was then
removed quantitatively from the adsorption medium by centrifu-
gation and the adsorption capacity of the hydrogel was determined
by estimating the residual Cd2+ in the exhausted adsorbate
solution. The Cd2+ adsorbed onto the hydrogel adsorbent were
desorbed from the hydrogel by stirring the latter using magnetic
stirrer for 240 min in 200 ml of 0.1 M HCl solution. The regenerated
hydrogel adsorbent was separated from the desorption solution by
centrifugation. The regenerated hydrogel adsorbent was washed
thoroughly several times with distilled water to remove any excess
HCl, and then dried in an oven at 60 °C for reuse. The adsorption–
desorption cycle was repeated consecutively for six times, and the
adsorption capacity and recovery ratio of the regenerated hydrogel
adsorbent was determined after each cycle. Scheme 1 represents a
model for Cd2+ ion desorption and the hydrogel regeneration. Fig. 1. Effect of crosslinking extent on the swelling capacity of the hydrogel.
4 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8
Fig. 2. Effect of curing temperature on the swelling capacity of the hydrogel.
3.1.3. Effect of crosslinking extent on the mechanical properties of the
hydrogel
Mechanical properties of the hydrogel such as the tensile
strength is considered to be one of the important factors that gov-
ern the handling of the hydrogel and its application in different
fields. Fig. 3 shows the effect of the crosslinking extent for the
hydrogel on its tensile strength. It is quite clear from the figure that
increasing the extent of crosslinking, expressed in terms of ECH
concentration, during the hydrogel preparation, is accompanied
by continuous increase in the hydrogel tensile strength. This is
obvious because as the extent of crosslinking increases, the poly-
mer chains of the hydrogel are bound to each other more strongly,
leading to improvement in the tensile strength.
3.1.4. Chemical structure of the hydrogel
FTIR spectroscopic analysis was carried out for poly(acrylic
acid)/starch graft copolymer before and after crosslinknig to prove
the chemical structure and to confirm the crosslinknig reaction.
Fig. 4 present the FTIR spectra of poly(acrylic acid)/starch graft
copolymer before crosslinking (4a) and after ECH-crosslinking
(4b). Both spectra showed the following bands: The band between
3404 cm1 represents OAH stretch; the absorption shoulder at
about 2926 cm1 represent CAH stretch and these are the two
main bands characteristic for starch. In addition, there are in both
spectra absorption bands at 1730–1650 cm1 characteristic for the
C@O stretch of carboxyl group coming from the grafted polyacrylic
acid. The difference between the two spectra is the presence of the
peaks at 1327 and 1262 cm1 in the chart (4b). These bands belong
to the stretching vibration of CAOAC and stretching vibration of
CAC respectively, for the crosslinking agent epichlorohydrin.
3.2. Cd2+ adsorption onto the crosslinked hydrogel
3.2.1. Effect of hydrogel graft yield on Cd2+ adsorption
Carbohydrate polymers, with their anhydroglucose units
repeated thousands of times along their backbones, are considered
to be ideal for heavy metals removal because these anhydroglucose
units contain large number of active functional groups capable of
Fig. 3. Effect of crosslinking extent on the mechanical properties of the hydrogel.
complexation with the metal ions. In these complexes, the linkage
between the metal ion and the functional group of the carbohy-
drate polymer is mainly of the coordination type. Owing to the
physical nature of hydrogels, with their network structure, they
have strong capacity to absorb the metal ions from their aqueous
solutions and transfer them to the gel phase resulting in ion
adsorption. Metal removal mechanism for any hydrogel is a combi-
nation between simple adsorption processes and ion exchange
processes and this depends on the physical structure of the hydro-
gel and the chemical nature of functional groups it has [37]. To
investigate the role of graft yield in improving the adsorption
capacity of the hydrogel, crosslinked PASGC samples with different
graft yield percents ranging from 0% to 40% were tried in removing
Cd2+ ion from its aqueous solution. It was found (Fig. 5) that the
percent Cd2+ removal increases by increasing the percent graft
yield. This can be attributed to the fact that increasing the graft
yield percent is accompanied by increase in the density of the
adsorption sites (carboxyl groups) introduced during the grafting
process, which will be available for metal ions adsorption. The
increment in percent metal ion removal by increasing the graft
yield percent is of course because polyacrylic acid chains which
are introduced to the starch back bone during the grafting process
contain large number of carboxyl groups which have salt formation
ability with metal ions; this is of course in addition to the physical
adsorption potential of starch molecule itself.
3.2.2. Adsorption studies
3.2.2.1. Effect of agitation time on Cd2+ percent removal. Fig. 6 pre-
sents the enhancement in Cd2+ percent removal by increasing the
agitation duration during the adsorption Cd2+ of ions by PASGC
hydrogel. The adsorption process was carried out using a metal
ion concentration of 150 mg/l together with hydrogel concentra-
tion of 2 g/l. It is quite clear from Fig. 6 that the adsorption process
shows quite rapid initial rate, leading to high metal removal per-
cent during the first 60 min from the adsorption duration. Almost
about 70% of the ultimate metal removal process is achieved with-
in the first 60 min of the agitation duration, and then the percent
metal removal starts to slow down until the adsorption reaches
its equilibrium state after 180 min at 100% percent removal. The
curve representing adsorption of Cd2+ by PASGC is shown to be
continuous and single, which indicates formation of monolayer
of Cd2+ onto the surface of the PASGC hydrogel adsorbent during
the adsorption process. It can be concluded from the good metal
ions uptake of the adsorbent and from the time needed to establish
the equilibrium in the adsorption process that PASGC hydrogel is
effective adsorbent for wastewater treatment. The high metal ion
removal during the first stage of the adsorption process is attrib-
uted to the high availability of the adsorption sites at this first
stage. The slow metal ion removal percent during the late stage
of the adsorption may be due to formation of metal ions aggregates
around the active sites of the adsorbent, which of course creates a
case of saturation of the adsorbent surface by the metal ions, lead-
ing to hindering the migration and diffusion of the metal ions from
the adsorbate phase to the adsorbent surface.
3.2.2.2. Effect of adsorption temperature. To study the effect of
temperature on percent metal ion removal, the adsorption process
was carried out using 0.2 g PASGC hydrogel immersed in 100 ml of
metal ion solution having concentration 150 mg/l. Four adsorption
trials were carried out under different temperatures conditions,
ranging from 30 °C to 60 °C. Fig. 7 demonstrates the effect of tem-
perature on the percent metal ion removal and as shown from the
figure, it is clear that the percent metal ion removal shows decre-
ment in its value by raising the adsorption temperature from 30 °C
to 60 °C. The decrease in adsorption by increasing the adsorption
medium temperature demonstrates clearly that the nature of the
 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8 5

Fig. 4. FTIR-Spectra of poly(acrylic acid)/starch graft copolymer: (a) before crosslinking and (b) after ECH-crosslinking (the hydrogel).

Fig. 5. Effect of percent graft yield on Cd2+ removal. Fig. 6. Effect of agitation duration on percent Cd2+ removal.

adsorption process is exothermic, and that the decrease in the

adsorption can be interpreted in terms of the tendency of metal 3.2.2.3. Effect of adsorbent concentration. To study the effect of
ions at high temperature to migrate from the adsorption phase adsorbent concentration on the percent metal ion removal, nine
to solution phase. adsorption trials were carried out by changing the adsorbent con-
6 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8
Fig. 7. Effect of adsorption temperature on percent Cd2+ removal.
centration from 0.2 g/l to 5 g/l at fixed temperature of 30 °C. The
used adsorbate concentration in all nine trials was 150 mg/l Cd2+
ions and the results of metal removal are illustrated in Fig. 8. As
is clear in Fig. 8, the curve is composed of two stages. The first stage
shows sharp increase in metal ion removal percent by increasing
the adsorbent dose from 0.2 g/l until 2 g/l. The second stage of
the curve shows steady state of metal ion removal, whatever the
concentration of the adsorbent is. The first stage of the curve shows
the great effect of the adsorbent concentration on the percent
metal ion removal and this interpreted in terms of increased sur-
face area of the adsorbent and accordingly increased number of
active sites available for metal ion adsorption. The second stage
of the curve reflects the fact that 2 g/l adsorbent concentration is
enough to achieve 100% metal ion removal and above this adsor-
bent concentration, no metal ions will be available for adsorption.
3.2.2.4. Effect of initial metal ion concentration. The moment at
which the adsorption process reaches its state of equilibrium, the
adsorbate molecules will be distributed reversibly between both
the liquid phase and the solid phase and this equilibrium appears
clearly when plotting the adsorption isotherm. In order to find
the suitable model which represents the best adsorption data
fitting, the data of the adsorption process are fitted to different iso-
therm models and by analysis of the isotherm data, one can assign
which model is more suitable for the adsorption process. To show
how the initial metal ion concentration can affect the efficiency of
the adsorption process, six adsorption trials were carried out, keep-
ing the adsorbent concentration constant at 2 g/l and constant
temperature of 30 °C and the initial metal ion concentration was
varied in these trial between 100 mg/l and 1500 mg/l. Fig. 9 is a
mathematical representation of the relationship between the
metal ion concentration in the liquid phase at the thermodynamic
equilibrium state (Ce) and the uptake of the metal ion per the
unit mass of the adsorbent (qe). It is quite clear from the figure
that the adsorbed amount of metal ion per unit weight of
the adsorbent shows noticeable increment in the first stage of
the curve, that it was 150 mg/g when using initial metal ion
Fig. 8. Effect of adsorbent dose on percent Cd2+ removal.
concentration of 200 mg/l and increased to be 496 mg/g by
increasing the initial metal ion concentration to 750 mg/l. These
findings are in complete accordance with the findings reported
elsewhere by other authors [38,39]. The enhancement in the
adsorption process during the first stage is interpreted in terms
of available adsorption sites and higher interaction between the
adsorbent sites and the adsorbate molecules. In addition, there will
be low resistance and accordingly higher diffusion rate of the metal
ions to the adsorption sites at higher concentrations of the metal
ion amount that leads to increased metal ion uptake. However, in
the second stage of the adsorption curve, when the initial metal
ion concentration was increased above 750 mg/l, it was noticed
that this increment did not lead to remarkable improvement in
the metal ion uptake, and this can be attributed to much saturation
of the available adsorption sites at high initial metal ion
concentration.
3.2.3. Adsorption isotherms
Langmuir isotherm and Freundlish isotherm are the most
famous mathematical fitting for the adsorption data, that these
isotherms relate the adsorption density (amount of metal ion
adsorbed per unit mass of the adsorbent), symbolized as qe to
the equilibrium concentration of the adsorbate in the bulk of the
liquid phase, symbolized as Ce.
3.2.3.1. Langmuir isotherm. The Langmuir fitting of the adsorption
data is based on the fundamental assumption that the case of max-
imum adsorption is attained when the active sites of the adsorbent
surface are completely covered and saturated with a monolayer of
the adsorbate molecules. At this stage the energy of adsorption is
assumed to remain always constant, and there will not be any
expected diffusion and migration of adsorbate molecules in the
plane surface between the liquid adsorbate phase and the solid
adsorbent phase. Langmuir treatment [40] was applied to the
adsorption of Cd2+ onto PASGC hydrogel as an adsorbent at
the equilibrium state and the results are presented in Fig. 10. The
mathematical representation of Langmuir isotherm is shown in
Eq. (1)
Ce Ce 1
¼ þ ð1Þ
qe Q o Q o  b
where Ce represents the concentration of the adsorbate (mg/l), at
the equilibrium state, the value of qe represents the amount of
metal ion adsorbed by unit mass of the adsorbent (mg/g) and Qo
and b are two Langmuir constants representing, respectively the
maximum adsorption capacity of the unit mass of the adsorbent
(mg/g) and the adsorption energy (l/mg).
According Langmuir, the plot of (Ce/qe) versus Ce, gives straight
line having a slop equal to the reciprocal of Qo and its intercept
equal to the reciprocal of (Qo⁄b). The values of Langmuir constants
were calculated for the adsorption of Cd2+ metal ions onto PASGC
Fig. 9. Effect of initial metal ion concentration on the Cd2+ uptake.
 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8 7

Table 2
Effect of separation factor, RL on isotherm shape.

RL value Type of isotherm

RL > 1 Unfavorable
RL = 1 Linear
0 < RL < 1 Favorable
RL = 0 Irreversible

Table 3
RL values based on Langmuir equation for adsorption of Cd2+ onto
hydrogel at 30 °C.
Fig. 10. Langmuir isotherm of Cd2+ adsorption by the hydrogel.
Cd2+ initial concentration (mg/l) RL values
200 0.32
300 0.23
Table 1
400 0.19
Langmuir constants for Cd2+ sorption onto hydrogel at 30 °C.
750 0.11
Langmuir constants 1000 0.08
1500 0.06
Qo (mg/g) b (l/mg) R2
588 0.01086 0.9957

When the values of log qe are plotted against the values of log Ce
a straight line is obtained. The slope of this straight line is the re-
hydrogel at 30 °C and the results are presented in Table 1. The
ciprocal of the value of n and its intercept corresponds to log KF.
maximum adsorption capacity of the crosslinked hydrogel (Qo)
Fig. 11 represents the Freundlich isotherm for Cd2+ metal ions
was found to be 588 mg Cd2+/1 g hydrogel. Other papers reported
adsorption onto PASGC hydrogel adsorbent. The values of Freund-
some maximum adsorption capacities for different hydrogels, as
lich constants for the adsorption process are calculated and listed
for example semi-IPN hydrogel based on chitosan and gelatin,
in Table 4. The value of n, calculated from the straight-line equa-
which has Qo value of 261 mg/g [40] and TEMPO-oxidized cellulose
tion is 2.598, which is higher than zero and lower than ten and this
hydrogel, which has Qo value of 268.2 mg/g [41].
indicates that the adsorption of Cd2+ onto PASGC hydrogel adsor-
The equilibrium parameter, RL, is a dimensionless constant or
bent is favorable from the thermodynamic point of view. The value
separation factor and it gives detailed information about the type
of the correlation coefficient, R2 for the adsorption process was
of isotherm [42]. This separation factor is defined Eq. (2)
found to be 0.9687. This value of R2 gives strong indicating that
RL ¼ 1=ð1 þ bC o Þ ð2Þ the adsorption process obey the Freundlich adsorption isotherm.

where Co is the initial metal ion concentration in the adsorption

solution (mg/l).
The separation factor, RL determines the shape of the isotherm
according to Table 2. The values of RL were calculated for the
adsorption of Cd2+ onto PASGC hydrogel by use of varying initial
Cd2+ concentrations ranging from 200 mg/l to 1500 mg/l and the
calculated values for RL are given in Table 3.
As is evident from Table 3, all RL values for all initial cadmium
ion concentration lay between 0.32 and 0.06 and since all these
values are greater than 0 and lower than 1, one can say that
the adsorption of Cd2+ onto PASGC hydrogel as adsorbent is a
favorable process. Moreover the value of the correlation coefficient
(R2) for the adsorption process is 0.9957, which indicate the data of
the adsorption process fitted well to Langmuir isotherm, or in other
words the adsorption of Cd2+ onto PASGC hydrogel obeys Langmuir
isotherm.
3.3. Cd2+ desorption and hydrogel regeneration
Regeneration of the adsorbent and recovery of the adsorbed
species are significant aspects in a successful adsorption process,
especially that there is strong emphasis on waste minimization,
recovery and reuse. Adsorbents that are characterized by better
regeneration and better recovery capacity for metal ions are
desirable from the cost of usage and recovery of valuable metals
points of view. The Cd2+ ions adsorbed onto the hydrogel adsor-
bent could be easily desorbed from the adsorbent hydrogel by
diluted HCl solution to recover the cadmium in the form of
CdCl2 salt. Fig. 12a and b show the adsorption capacity and
percent recovery of hydrogel adsorbent samples, desorbed or

3.2.3.2. Freundlich isotherm. The data of Cd2+ metal ion adsorption

onto PASGC hydrogel adsorbent was also fitted to Freundlich
adsorption isotherm to show whether the adsorption process obey
this adsorption model or not. Freundlich isotherm equation [43]
relates the amount of adsorbate molecules adsorbed by unit mass
of the adsorbent (qe) to the adsorbate concentration at the equilib-
rium state (Ce), as represented by Eq. (3)
log qe ¼ log K F þ ð1=nÞ log C e ð3Þ
where KF (mg/g) represents the maximum capacity of the adsorbent
(the maximum amount of Cd2+ ions adsorbed by unit mass of
PASGC hydrogel) and n is Freundlich constant, which gives an
indication about the favorability of the adsorption process. Fig. 11. Freundlich isotherm of Cd2+ adsorption by the hydrogel.
8 E.S. Abdel-Halim, S.S. Al-Deyab / Reactive & Functional Polymers 75 (2014) 1–8
Table 4
Freundlich constants for Cd2+ adsorption onto hydrogel at 30 °C.
Freundlich constants
KF (mg/g) n R
45.73 2.598
Fig. 12. Effect of consecutive adsorption–desorption cycles on (a) hydrogel
adsorption capacity and (b) percent recovery of the hydrogel.
regenerated for six consecutive cycles. It is clear from Fig. 12a
that the adsorption capacity of the hydrogel adsorbent decreases
with the consecutive repeating of the adsorption–desorption cy-
cles. This means decrease in the percent recovery of the hydrogel
adsorption capacity by consecutive regeneration cycles as shown
in Fig. 12b, the percent recovery was 93.8% after the first desorp-
tion cycle and decreased to 58.7% after the sixth cycle.
Acknowledgement
The authors extend their appreciation to the Deanship of Scien-
tific Research at King Saud University for funding the work through
the research group Project No. RGP-VPP-029.
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