Colloids and Surfaces A: Physicochem. Eng.

Aspects 441 (2014) 5158

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Colloids and Surfaces A: Physicochemical and
Engineering Aspects
j our nal home page: www. el sevi er . com/ l ocat e/ col sur f a
pH dependence and thermodynamics of Hg(II) adsorption onto
chitosan-poly(vinyl alcohol) hydrogel adsorbent
Xiaohuan Wang
a,1
, Ruzhong Sun
b,
, Chuanyi Wang
a,
a
Key Laboratory of Functional Materials and Devices for Special Environments of CAS, Xinjiang Technical Institute of Physics & Chemistry of CAS, 40-1
South Beijing Road, Urumqi 830011, PR China
b
College of Chemistry and Pharmacy Engineering, Nanyang Normal University, 1638 Wolong Road, Nanyang 473061, PR China
h i g h l i g h t s

CTS-PVA hydrogel adsorbent showed

superior adsorption properties for
Hg(II) ions.

pH inuence and theromodynamics

of Hg(II) adsorption on the hydrogel
adsorbent was studied.

Functional groups responsible for

Hg(II) adsorption changed with the
pH of solutions.

The binding force between Hg(II) and

functional groups was strengthened
at high temperatures.

Results obtained in this study may

provide a scientic and engineering
basis for Hg(II) removal.
g r a p h i c a l a b s t r a c t
a r t i c l e i n f o
Article history:
Received 2 June 2013
Received in revised form25 August 2013
Accepted 29 August 2013
Available online 6 September 2013
Keywords:
pH dependence
Thermodynamics
Chitosan/poly(vinyl alcohol) hydrogel
adsorbent
Hg(II)
Adsorption
a b s t r a c t
The chitosan/poly(vinyl alcohol) (CTS-PVA) hydrogel adsorbent with three-dimensional network struc-
ture showed superior adsorption properties for Hg(II) ions. The pH inuence study showed Hg(II)
adsorption on the hydrogel adsorbent is strongly pH-dependent. The adsorption capacity in pH 2.00
solution (200.20 mg/g) is higher than that in pH11.00 solution (140.27 mg/g), which indicated that Hg(II)
adsorption on the hydrogel adsorbent was not only by electrostatic interactions. FT-IR spectral analysis
before and after Hg(II) adsorption represented that the functional groups responsible for Hg(II) adsorp-
tion changed with the pH of solutions. Thermodynamic studies revealed that Hg(II) adsorption on the
hydrogel adsorbent is a favorable, spontaneous, and endothermic chemisorption process. The binding
force between Hg(II) ions and functional groups was strengthened at high temperatures, which made
the adsorption more favorable at high temperatures. The adsorption process tted well by the Langmuir
and the Freundlich isotherm models. The Langmuir maximum adsorption capacity increased from 697.70
to 950.62 mg/g with increasing temperature from 20 to 60

C. This study will contribute to an in-depth

understanding of adsorption phenomena, and provide a scientic and engineering basis for the practical
application of the CTS-PVA hydrogel adsorbent.
2013 Elsevier B.V. All rights reserved.

Corresponding author. Tel.: +86 377 63525056.

Corresponding author. Tel.: +86 991 3835879; fax: +86 991 3838957.
E-mail addresses: wxh0377@ms.xjb.ac.cn (X. Wang), nysrzh@163.com(R. Sun),
cywang0991@163.com(C. Wang).
1
Tel.: +86 991 3835879; fax: +86 991 3838957.
1. Introduction
All mercury compounds are known to be highly toxic chemicals.
Inorganic mercury has been reported to produce harmful effects
in culture medium at 5g/L. It exists in two ionic states: Hg(I)
and Hg(II). Hg(II) or mercuric salts, are much more common in
the environment than Hg(I) or mercurous salts [1]. Hg(II) can be
0927-7757/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.08.068
52 X. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 5158
methylated by reducing bacteria in anoxic habitats and trans-
formed into methylmercury (MeHg
+
or Me
2
Hg). So, it is considered
as the most toxic formof mercury [2]. Recently, great efforts have
been made to develop methods that can effectively remove Hg(II)
ions fromwastewater, andat the same time, recover its compounds
in a more concentrated form to avoid the second pollution after
removing them from the water [3]. The use of adsorbents pos-
sessing selectivity toward Hg(II) ions makes good contributions
to achieving this target. Polymer adsorbents containing ligands
such as nitrogen-containing functional groups are often used in the
selective removal of Hg(II) fromaqueous solutions [46].
Chitosan (CTS), a copolymer that is primarily composed
of (14) linked 2-amino-2-deoxy-d-glucopyranose units, and
residual 2-acetamido-2-deoxy-d-glucopyranose units, is a biopoly-
mer of the most widely studies on heavy metal removal. It shows
outstanding adsorption capacity for Hg(II) ions ranging from 430
to 1127mg/g especially in pH close to neutral, due to the presence
of large number of functional groups (acetamido, primary amino
and/or hydroxyl groups) with high chemical reactivity in its chem-
ical structure [5,7,8]. However, the protonation of amino groups
results in CTS dissolution in acidic solutions, which limits CTS to be
used as an adsorbent in acidic media. In addition, the amine groups
of CTS do not have good adsorption selectivity for different metal
ions [9]. All of these determine CTS is not a satisfying adsorbent for
the selective removal of Hg(II) ions fromwastewater [10].
Poly(vinyl alcohol) (PVA), a semicrystalline hydrophilic poly-
mer, is usually used to blend with CTS to obtain a variety of
materials with good mechanical and chemical properties, such as
hydrogels [11,12], blend foams [13], blend/composite membranes
or lms [14], blend beads [15,16], etc. The addition of PVA can
improve the mechanical property and reduce the brittleness of the
dried sample. Meanwhile, hydroxyl groups in PVA polymer struc-
ture may contribute to the adsorption for heavy metal ions. These
materials have been widely studied in the removal of heavy metal
ions such as lead, copper, silver and cadmium ions from water
or wastewater [11,12]. However, little attention has been paid to
investigating their adsorption characteristics for mercury ions.
Our previous studies showed that the CTS-PVA hydrogel adsor-
bent prepared by a glutaraldehyde cross-linking in combination
with an alternate freeze-thawed process demonstrated superior
adsorption properties for Hg(II) ions [17]. The hydrogel adsor-
bent contains NH
2
, NHCOCH
3
and C N groups as well as OH
groups. It can selectively adsorb Hg(II) ions frommulti-component
solutions with high efciency. The CTS-PVA hydrogel adsorbent
containing 30wt.% PVA showed moderate mechanical property,
excellent adsorption properties, and the most important is, it had
no leaching in solutions. So, it was thereby selected as an objective
adsorbent for typical adsorption experiments in the present work.
The present work focused on the pH dependence and adsorption
mechanisms of the CTS-PVA hydrogel adsorbent for Hg(II) ions in
different pHsolutions, as well as the detailedadsorptionthermody-
namics. This study will contribute to an in-depth understanding of
adsorption phenomena and open up an effective way for mercury
removal fromwater.
2. Experimental
2.1. Materials
CTS (industrial grade, the degree of deacetylation was 75%,
and the average molecular weight was 310
5
g/mol) was pur-
chased fromZhejiang Golden-Shell Biochemical Co. Ltd. (Zhejiang,
China). PVA(industrial grade, the degree of hydrolysis was 99% and
the average degree of polymerization was 1700) was provided by
Lanzhou Xinxibu Vinylon Company Ltd (Gansu, China). Glutaralde-
hyde with a concentration of 25%, mercuric acetate and other
chemicals wereof analytical gradeandcommerciallyobtainedfrom
Tianjin Kermel Chemical Reagent Co., Ltd (Tianjin, China). Aqueous
solutions were all prepared with Millipore water (18.25M/cm).
2.2. Preparation
The CTS-PVA hydrogel adsorbent with a three-dimensional net-
work structure was prepared according to our previous report [17].
Its schematic network structure and the digital photo of the dried
sample were showninFig. 1. The sample usedfor adsorptionexper-
iments was milled and sieved through an 80-mesh screen.
2.3. Adsorption experiments
The adsorption experiments were carried out by adding certain
amount of thedriedsampleintoasimulatedwastewater containing
Hg(II) ions at a desirable concentration and pH value, and then the
mixture was shaken in a thermostatic shaker bath at an appropri-
ate temperature until the adsorptiondesorption equilibriumwas
established. The pH of solutions was adjusted by the dilute acetic
acid or sodium hydroxide solution and measured by a pH meter
(Mettler Toledo 320).
For investigating the effect of the initial pH(pH
0
) of solutions on
adsorption, a pH range from2.00 to 11.00 was selected, and a con-
centrationof 85.56mg/L was selectedas the initial concentrationof
Hg(II) solution to avoid precipitation of Hg(II) ions. For equilibrium
adsorption experiments at different temperatures (20, 30, 40, 50
and 60

C), Hg(II) solutions with a concentration range fromabout

500mg/L to 2500mg/L were used, and the mixture was shaken in
a thermostatic shaker bath for 24h to ensure the equilibriumto be
established.
The concentration of mercury in solutions was determined by
anatomic uorescence spectrophotometer (AF-640, Beijing Beifen-
gruili Analytical Instrument Co., China). The adsorption capacity of
the adsorbent sample for Hg(II) ions at a given time t or at equilib-
riumcan be derived using the following equation:
q =
(C
0
C) V
m
, (A.1)
where q is the amount of Hg(II) adsorbed at time t or at equilibrium
(mg/g), C
0
is the initial Hg(II) concentration (mg/L), C is the Hg(II)
concentration at time t or at equilibrium (mg/L), m is the mass of
the adsorbent used (g) and V is the volume of Hg(II) solution used
(L).
2.4. Characterization
2.4.1. The determination of the isoelectric point (pI)
The isoelectric point (pI) of the CTS-PVAhydrogel adsorbent was
determined by the solid addition method [18]. 0.1mol/L NaCl solu-
tion was used as electrolytic solution in this study. The pH value
of the solution was adjusted with 0.1mol/L NaOH or 0.1mol/L HCl
solutions to cover a range from 2 to 12 in approx 2pH unit incre-
ments. To 25mL NaCl solutions with the desired initial pH value
(pH
0
), 0.1000g CTS-PVA hydrogel adsorbent samples were added.
Thenthe conical asks were securely cappedimmediately. The sus-
pensions were manually shaken and allowed to equilibrate for 48h
with intermittent manual shaking at room temperature. The nal
pH value (pH
f
) of each supernatant uid was determined again.
By plotting the difference between the pH
0
and the pH
f
(i.e., pH,
which equals pH
0
minus pH
f
) versus pH
0
, a curve can be obtained.
The pH value which is corresponding to pH=0 in the resulting
curve is the pI of the sample.
X. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 5158 53
Fig. 1. Schematic structure (A) and digital photo (B) of the CTS-PVA hydrogel adsorbent.
2.4.2. Fourier transforminfrared spectroscopy (FTIR)
The FTIR spectra of the CTS-PVA hydrogel adsorbent before and
after Hg(II) adsorption were recorded using a Fourier transform
infrared spectrometer (FTS-165, BIO-RAD, USA). All the samples
were prepared as potassiumbromide tablets, and the range of the
scanning wavenumbers was 5004000cm
1
.
2.4.3. Surface area analysis
The surface area of the CTS-PVA hydrogel adsorbent were ana-
lyzed by a nitrogen adsorptiondesorption method at 77K using
a surface area analyzer (Micromeritics, ASAP 2020). The pretreat-
ment conditions are 105

C and vacuum for 3h. The surface area

was calculated by the BrunauerEmmertTeller (BET) equation.
3. Results and discussion
3.1. pH dependence and adsorption mechanisms of the hydrogel
adsorbent for Hg(II) ions
3.1.1. Effect of the pH
0
of solution on adsorption
The determination of the isoelectric point (pI) of an adsorbent is
necessary for further elucidating the adsorption mechanism. So, a
preliminary test of pI was determined by the solid addition method
[18]. Result showed that the pI of the sample was 7.85. Therefore,
in the solution of pH value below 7.85, the particle surface of the
hydrogel adsorbent is positively charged. Otherwise, the surface is
negatively charged [18].
The effect of the pH
0
of solution on Hg(II) adsorption was
shown in Fig. 2. The pH-dependent curve showed two peaks
and a minimum, which revealed the strong pH-dependence of
Hg(II) adsorption on the hydrogel adsorbent. Previous study about
lead (II) adsorption on CTS-PVA hydrogel bead also showed a
similar phenomena [12]. The adsorption capacity in pH 2.00
solution (200.20mg/g) is higher than that in pH 11.00 solution
(140.27mg/g), whichindicatedthat Hg(II) adsorptiononthe hydro-
gel adsorbent was not only by electrostatic interactions, because
that, the positively charged surface of the adsorbent in pH 2.00
solution was not as favorable as the negatively charged surface
in pH 11.00 solution for the adsorption of Hg(II) cations. The high
adsorption capacity of the adsorbent in pH 2.00 solution also indi-
cated that there must be more than one mechanismresponsible for
Hg(II) adsorption on the hydrogel adsorbent. Our previous study
has revealed that both chelation and ion exchange contributed to
Hg(II) adsorption on the CTS-PVA hydrogel adsorbent [17].
3.1.2. Analysis of adsorption mechanisms under different pH
conditions
In order to further illustrate the nature of Hg(II) adsorption on
the hydrogel adsorbent under different pH conditions, FT-IR spec-
tra of the dried sample before and after adsorption in different pH
solution were compared.
Firstly, we compared FT-IR spectra of the hydrogel adsorbent
before and after adsorption in pH 2.00 acetic acid and mercuric
acetate solutions, respectively (Fig. 3). It was found that, com-
pared with the FT-IR spectrum of the unloaded sample (Fig. 3a),
the FT-IR spectrumof the sample after adsorption in pH2.00 acetic
acid solution (Fig. 3b) showed several obvious spectral changes.
The characteristic peak of the N H stretching vibration situated
at about 3372cm
1
obviously shifted to the higher wavenum-
ber (3403cm
1
). Meanwhile, the characteristic peaks of the C O
stretching vibration (shifted from 1651 to 1635cm
1
), the N H
deformation vibration (shifted from 1598 to 1557cm
1
) and
the C N stretching vibration (shifted from 1420 to 1384cm
1
)
strongly shifted to the lower wavenumbers. These changes may be
caused by the binding of NH
2
and NHCOCH
3
groups with pro-
tons to formcomplexes (Eqs. (B.1) and (B.2)), and thereby leading
the surface of the sample to be positively charged [12].
R NH
2
+H
+
R NH
3
+
(B.1)
Fig. 2. pH
0
effect on the adsorption of the CTS-PVA hydrogel adsorbent for Hg(II)
ions. Adsorption experimentsC
0
: 85.56mg/L; sample dose: 0.0100g/50mL; the
range of pH
0
: 2.0011.00; temperature: 30

C; contact time: 24h.

54 X. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 5158
Fig. 3. FT-IR spectra of the unloaded CTS-PVA hydrogel adsorbent (a), the sample
after being dipped in pH 2.00 acetic acid solution (b) and the sample after Hg(II)
adsorption in pH 2.00 mercuric acetate solution (c), respectively.
NH CCH
3
O
+ H
+
CH
3
C
O
NH
2
+
R
R
(B.2)
Compared with FT-IR spectra of the unloaded sample (Fig. 3a)
and the sample after adsorption in pH 2.00 acetic acid solution
(Fig. 3b), the FT-IR spectrum of the adsorbent after adsorption
in pH 2.00 mercuric acetate solution (Fig. 3c) showed several
new changes. The characteristic peaks of the saccharide structure
stronglyshiftedtothelower wavenumbers. Meanwhile, thecharac-
teristic peak of the C H stretching vibration shifted to the higher
wavenumbers (2935cm
1
). These indicated that free pendant OH
groups in the polymer structure should interact with Hg(II) ions in
pH 2.00 mercuric acetate solution. The possible chemical reaction
was given as follows:
R

OH + Hg
2+
(R

OH)Hg
2+
or (R

OH)
2
Hg
2+
(B.3)
Despite that, several other spectral changes were observed in
Fig, 3c when compared with Fig. 3a. The characteristic peak corre-
sponding to the C O and C N stretching vibration shifted from
1651cm
1
to 1641cm
1
, which is not as obvious as that observed
inFig. 3b. This maybe indicate the interactionof NHCOCH
3
groups
and C N groups with Hg(II) ions, because that the C N group is a
milder basic ligand than NH
2
or OH groups and it can interact
with a very soft acid such as Hg(II) ions. The reaction between C N
groups and Hg(II) ions has been conrmed by our previous study
[17] and other related researches [19]. It was given as follows:
RCH N R' + (CH
3
COO)
2
Hg RCH HgOOCCH
3
R'
N
(B.4)
The characteristic peak of the N H deformation vibration in
Fig. 3c nearly disappeared completely when compared with Fig. 3b.
This may be due to the reaction between NHCOCH
3
groups and
Hg(II) ions, which was given as follows:
R NH CCH
3
+ (CH
3
COO)
2
Hg CH
3
C
O
N
R
HgOOCCH
3
or
CH
3
C N Hg N CCH
3
R
O O O
R
(B.5)
Secondly, we compared FT-IR spectra of the hydrogel adsorbent
before and after adsorption in different pH mercuric acetate solu-
tions (shown in Fig. 4). It can be seen that, compared with the FT-IR
spectrum after adsorption in pH 2.00 mercuric acetate solution
Fig. 4. FT-IR spectra of the unloaded CTS-PVA hydrogel adsorbent (a) and samples
after Hg(II) adsorption in different pH solutions (b: pH 2.00; c: pH 5.00; d: pH 7.00;
e: pH 9.00; f: pH 11.00).
(Fig. 4b), the FT-IR spectrum after adsorption in pH 5.00 mercuric
acetate solution (Fig. 4c) showed several more obvious changes.
Except for the obvious changes of the characteristic peaks of the
saccharide structure, C N groups and NHCOCH
3
groups, the
characteristic peaks of the N H stretching vibration obviously
shifted to the higher wavenumber (from 3398 to 3428cm
1
).
Meanwhile, the characteristic peaks of the C H stretching
vibration near 2935cm
1
and the C H symmetrical deformation
vibration at 1417cm
1
and 1381cm
1
evidently shifted to the
lower wavenumbers. These indicated that free pendant NH
2
groups may also interact with Hg(II) ions when the sample was
dipped in pH5.00 mercuric acetate solution. The possible chemical
reaction was given as follows:
2R NH
2
+Hg
2+
(R NH
2
)
2
Hg
2+
(B.6)
The FT-IR spectra after Hg(II) adsorption in pH 7.00 and 9.00
mercuric acetate solutions were very similar (Fig. 4d and e). Com-
pared with the FT-IR spectrum of the unloaded sample (Fig. 4a),
the obvious shifts of the FT-IR spectra after Hg(II) adsorption in
pH 7.00 and 9.00 mercuric acetate solutions mainly concentrated
on the characteristic peaks of the N H stretching vibration, the
C O stretching vibration, the N H deformation vibration and
the C Nstretching vibration. These indicated NH
2
, NHCOCH
3
,
and C Ngroups may all participate in Hg(II) adsorption under such
pH conditions.
Compared with Fig. 4a, the FT-IR spectrumafter Hg(II) adsorp-
tion in pH 11.00 (Fig. 4f) only showed an obvious shift of the
characteristic peak of the N H stretching vibration in NH
2
groups. This implied NH
2
groups may be the main functional
groups responsible for Hg(II) adsorption in pH 11.00 mercuric
acetate solutions. According to the research of Li and Bai [12], OH

ions can be adsorbed onto the surface of the CTS-PVA hydrogel

adsorbent through hydrogen bonds when the pH of solutions is
higher than its pI, and thereby lead to the surface of the adsorbent
negatively charged (Eq. (B.7)) [12].
R NH
2
+OH

R NH
2
. . .OH

(B.7)
So, in solutions which pH value is higher than the pI of the
adsorbent, the negative charged surface of the adsorbent will
facilitate Hg(II) ions being adsorbing by the electrostatic interac-
tion.
X. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 5158 55
Table 1
Parameters associated with Hg(II) adsorption on the CTS-PVA hydrogel adsorbent at different temperatures. (T: K; qm,exp: mg/g; KL: L/g; aL: L/mg; q
m,cal
: mg/g; S: m
2
/g; G:
kJ/mol; H: kJ/mol; S: kJ/(mol K); KF:L/mg.).
T qm,exp The Langmuir model S RL G H S The Freundlich model
KL aL q
m,cal
R
2
KF n R
2
293 697.70 7.0215 0.0092 763.36 0.9973 87.056 0.16300.0429 4.748 94.5606 0.2925 0.9979
303 723.87 10.8378 0.0141 769.23 0.9979 87.726 0.11280.0284 6.003 134.227 0.2492 0.9970
313 741.31 15.6397 0.0202 775.19 0.9984 88.405 0.08160.0200 7.156 48.183 0.179 173.1929 0.2174 0.9972
323 837.25 41.4079 0.0484 854.70 0.9987 97.473 0.03570.0084 9.999 307.7797 0.1532 0.9972
333 950.62 71.1238 0.0754 943.40 0.9976 107.590 0.02320.0054 11.806 401.7723 0.1319 0.9892
3.2. Adsorption thermodynamics
3.2.1. Adsorption isotherms
The adsorption isotherms of Hg(II) adsorption on the CTS-PVA
hydrogel adsorbent at different temperature were presented in
Fig. 5. The isotherm shapes are consistent with the favorable
adsorption equilibrium patterns proposed by Weber et al. [20].
This suggested the adsorption process of Hg(II) adsorption on the
hydrogel adsorbent should be a favorable process. Such anticipa-
tionwas also conrmedby the equilibriumparameter R
L
calculated
in the following section. The increase of the adsorption capacity
with increasing temperature indicated that the adsorption process
of theCTS-PVAhydrogel adsorbent for Hg(II) ions was endothermic.
3.2.2. Adsorption isothermanalysis
Theanalysis of isothermdatais veryimportant for developingan
equationwhichcanaccurately represent the results andbe usedfor
design purposes. The adsorption data obtained in this study were
analyzed by the well-known and widely applied isothermmodels,
namely, the Langmuir and the Freundlich isothermmodels.
The Langmuir model. The Langmuir model is perhaps the most
straightforward non-linear isotherm model. It is predicated on
the assumptions that the energy of sorption for each molecule is
the same and independent of surface coverage. And that sorption
occurs only on localized sites and involves no interactions between
adsorbed molecules [20]. The Langmuir model is usually expressed
as follows [21]:
q
e
=
x
m
=
K
L
C
e
(1 +a
L
C
e
)
, (A.2)
where x is the amount of Hg(II) ions adsorbed(mg), mis the amount
of adsorbent used (g), C
e
(mg/L) and q
e
(mg/g) are the liquid phase
Fig. 5. Adsorption isotherms of Hg(II) adsorption on the CTS-PVA hydrogel
adsorbent at different temperatures. Adsorption experimentsthe range of C
0
:
02500mol/L; sample dose: 0.0500g/25mL; pH
0
: 5.50; the range of temperature:
2060

C; contact time: 24h.

concentration and solid phase concentration of Hg(II) ions at equi-
librium, respectively.
At low surface coverage, the Langmuir isotherm reduces to a
linear relationship. The most common linear formof the Langmuir
model is formulated as:
C
e
q
e
=
1
K
L
+(
a
L
K
L
)C
e
, (A.3)
where K
L
(L/g) and a
L
(L/mg) are the Langmuir isothermconstants,
respectively, and a
L
relates to the energy of adsorption. When C
e
/q
e
is plotted against C
e
, a straight line will be obtained. The value of K
L
can be obtained fromthe intercept which is 1/K
L
, and the value of
a
L
can be obtained from the slope which is a
L
/K
L
. The maximum
adsorption capacity of the adsorbent, q
m,cal
, i.e., the equilibrium
monolayer capacity or saturation capacity, is numerically equal to
K
L
/a
L
. The Langmuir parameters of Hg(II) adsorption on the CTS-
PVA hydrogel adsorbent at different temperatures were listed in
Table 1.
From Table 1, it can be seen that the linear correlation
coefcients (R
2
) at different temperatures are all close to 1. This
indicated that the adsorption process tted well with the Langmuir
model. So, it can be considered that Hg(II) ions were adsorbed with
a monolayer on the particle surface of the adsorbent. The Langmuir
maximum adsorption capacity (q
m,cal
) increased from 697.70 to
950.62mg/g with the temperature of solutions increasing from20
to 60

C, which reected the endothermic nature of the adsorption

process again. Compared with other adsorbents (Listed in Table 2)
[2229], the Langmuir maximum adsorption capacity of the CTS-
PVA hydrogel adsorbent are quite high. This indicated the CTS-PVA
hydrogel adsorbent is a superior adsorbent that can be used for the
removal of Hg(II) fromaqueous solutions. The value of a
L
increased
from0.0092L/mgto0.0754L/mgwithincreasingtemperaturefrom
20 to 60

C, which indicated the binding force between Hg(II) ions

Table 2
Acomparison of the maximumadsorption capacity of the adsorbents for Hg(II) ions.
Adsorbent Maximumadsorption
capacity (mg/g)
Source
Chitosan adsorbent (which is
crosslinked with glutaraldehyde)
145 (25

C) [22]
Modied magnetic chitosan
adsorbents (which is crosslinked with
glutaraldehyde and functionalized
with magnetic nanoparticles (Fe
3
O
4
))
152 (25

C) [22]
The polyaniline/attapulgite (PANI/ATP)
composite
800 (25

C) [23]
A chitosanthioglyceraldehyde Schiffs
base cross-linked magnetic resin
(CSTG)
982 [24]
The cross-linked magnetic
chitosan-phenylthiourea (CSTU) resin
1353 [25]
The chitosanECH matrix 621.83 [26]
The polyaniline/humic acid composite 671 [27]
The PPyRGO composite 980 [28]
The ethylenediamine-modied
magnetic crosslinking chitosan
microspheres (EMCR)
539.59 [29]
56 X. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 5158
Fig. 6. Plot of RL against C
0
at different temperatures. Adsorption experimentsthe
range of C
0
: 02500mol/L; sample dose: 0.0500g/25mL; pH
0
: 5.50; the range of
temperature: 2060

C; contact time: 24h.

and functional groups of the hydrogel adsorbent was strengthened
at a higher temperature. This further substantiated the endother-
mic nature of the adsorption process.
The dimensionless constant separation factor or equilibrium
parameter, R
L
, is another factor that can express the essential fea-
tures of the Langmuir isotherm. It is dened by the following
relationship [30]:
R
L
=
1

1 +(K
L
/q
m
)C
0
. (A.4)
For favorable adsorption process, the value of R
L
should be
ranged from 0 to 1. If the value of R
L
is beyond 1, it implies that
the adsorption process is unfavorable. The value of R
L
of Hg(II)
adsorption on the CTS-PVA hydrogel adsorbent changed with C
0
was shown in Fig. 6, and the values of R
L
at different temper-
atures were given in Table 1. Values of R
L
were in the range of
01, which indicated the adsorption process of the hydrogel adsor-
bent for Hg(II) ions is favorable again. Values of R
L
decreased with
the increase of the temperature suggested the adsorption is more
favorable at high temperatures.
The Freundlich model. The Freundlich model is an empirical
equation and perhaps the most widely used nonlinear sorption
equilibriummodel. This model applies to adsorption onto hetero-
geneous surfaces with a uniformenergy distribution and reversible
adsorption. Moreover, this model is not restricted to the formation
of the monolayer. Thats to say, the amount of adsorbate adsorbed
on the adsorbent will increase in case of increasing the adsorbate
concentrationinthe solution. The Freundlichmodel has the general
formas follows [31]:
q
e
= K
F
C
n
e
, (A.5)
whereK
F
is theFreundlichconstant whichrelates tosorptioncapac-
ity(L/mg), nis theheterogeneityfactor whichrelates tothesorption
intensity. K
F
and n are empirical constants which is dependent on
several environmental factors. The value of n ranges from 0 to 1,
andindicates the degree of non-linearity betweenthe solutioncon-
centration and the adsorption. If the value of n is equal to 1, the
adsorption is linear. If the value is below1, the adsorption process
is chemical. If the value is above 1, the adsorption is a favorable
physical process. The more heterogeneous the surface, the closer
the value of n is to 0 [12,32].
For determination of these empirically derived constants, the
Freundlich model is usually expressed the logarithmic formas fol-
lows:
log (q
e
) = n log (C
e
) +log K
F
. (A.6)
K
F
and n can be determined fromthe slope and intercept of the
linear plot of log(q
e
) versus log(C
e
). The Freundlich parameters of
Hg(II) adsorption on the CTS-PVA hydrogel adsorbent at different
temperatures were listed in Table 1.
From Table 1, it can be seen that the linear correlation
coefcients (R
2
) at different temperatures are close to 1, which
indicated that the Freundlich model can also be used to describe
the adsorption process of the CTS-PVA hydrogel adsorbent for
Hg(II) ions. The values of n decreased from 0.2925 to 0.1318 with
increasing temperature from 20 to 60

C. This suggested that the

adsorption process of Hg(II) ions on the hydrogel adsorbent is
chemical, and the surface of the adsorbent is more heterogeneous
at high temperatures.
3.3. The specic surface area of the hydrogel adsorbent toward
Hg(II) ions binding
The Langmuir monolayer saturation capacity (q
m,cal
, mg/g) cal-
culated from the Langmuir equation (Eq. (A.3)), i.e., the ultimate
adsorption capacity at high concentrations, can be used to esti-
mate the specic surface area (S, m
2
/g) of the CTS-PVA hydrogel
adsorbent towardHg(II) binding, using the following equation[33]:
S =
q
m,cal
NA
1000M
, (A.7)
where N is Avogadro constant, 6.0210
23
mol
1
, A is the cross-
sectional area of metal ion (m
2
), M is the molar weight of
Hg(II) ions, 200.59g/mol. According to the radius of Hg(II) ion
(1.1010
10
m), the cross-sectional area of Hg(II) ion was cal-
culated to be 3.8010
20
m
2
. The specic surface areas of the
hydrogel adsorbent towardHg(II) bindingat different temperatures
were calculated and listed in Table 1.
From Table 1, it can be seen that the specic surface area of
the hydrogel adsorbent toward Hg(II) ions binding increased with
increasingtemperature. This indicatedthat Hg(II) adsorptiononthe
hydrogel adsorbent is chemisorption. The BET specic surface area
of the sample was determined to be 14.724m
2
/g, which is much
smaller than the binding specic surface area calculated. This fur-
ther conrmedthe chemisorptionnature of the adsorptionprocess.
3.4. Thermodynamic parameters
Withthe helpof equilibriumdata obtainedat different tempera-
tures, thermodynamic parameters suchas Gibbs freeenergychange
(G, J/mol), enthalpy change (H, J/mol) and entropy change (S,
J/(mol K)) of the adsorption process of the CTS-PVAhydrogel adsor-
bent for Hg(II) ions can be determined by Gibbs equation and Vant
Hoff equation listed as follows:
G = RT ln K
L
, (A.8)
ln K
L
=
H
(RT)
+
S
R
, (A.9)
where K
L
is the equilibrium constant obtained from the Langmuir
model (L/g), T is the absolute temperature (K), R is the universal gas
constant (8.314J/(mol K)). The values of H and S can be deter-
mined fromthe slope and the intercept of the plot of ln(K
L
) versus
1/T. Theplot andthermodynamic parameters of theadsorptionpro-
cess of the hydrogel adsorbent for Hg(II) ions were shown in Fig. 7
and Table 1, respectively.
X. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 5158 57
Fig. 7. The plot of ln(KL) versus 1/T.
The linear correlation coefcient (R
2
) obtained from Fig. 7 was
0.9807. It is very close to 1. Such a good linear relationship made
the calculation of the values of H and S according to Eq. (A.9)
possible.
The values of G are all negative at all temperatures. This indi-
cated that the adsorption process was spontaneous. The reduced
values of G with increasing the temperature suggested the spon-
taneous nature is improved at higher temperature. The positive
value of H suggested the adsorption process was an endothermic
process. The positive value of S indicated the entropy of the sys-
temincreasedafter adsorption, that is to say, the randomness at the
solidliquid interface increased. This unusual phenomenon may be
owing to the fact that the desolvation disturbs the structure of the
reaction medium and promotes the disorganization of the system
during the formation process of complex. It was also observed by
Weber et al. [20] and Guerra et al. [34].
4. Conclusions
Hg(II) adsorption on the CTS-PVA hydrogel adsorbent is a favor-
able, spontaneous, and endothermic chemisorption process. The
pHof solution had a great effect on Hg(II) adsorption on the hydro-
gel adsorbent. The adsorption mechanisms and functional groups
responsible for Hg(II) adsorption changed with the pHof solutions.
In lower pH solutions, chelation between functional groups and
Hg(II) ions was the mainmechanism. Free pendant OHgroups and
C Ngroups as well as NHCOCH
3
groups were the main functional
groups responsible for Hg(II) adsorption. When pH of solution was
close to the pI of the hydrogel adsorbent, free pendant OH, NH
2
and NHCOCH
3
groups as well as C Ngroups all involved in Hg(II)
adsorption. While in solutions which pHwas much higher than the
pI of the hydrogel adsorbent, electrostatic interaction played an
important role. Both chelation and electrostatic interaction made
contributions to Hg(II) adsorption, and free pendant NH
2
groups
became the main functional groups responsible for Hg(II) adsorp-
tion. The binding force between Hg(II) ions and functional groups
was strengthened at higher temperature, and thereby the adsorp-
tion was more favorable at high temperature. Hg(II) adsorption on
the hydrogel adsorbent canbe well explainedby boththe Langmuir
and the Freundlich isothermmodels.
Acknowledgements
This work is nancial supported by the Western Light Pro-
gram of the Chinese Academe of Sciences (XBBS201116), the
National Natural Science Foundation of China (21107133), and the
One Hundred Talents program of Chinese Academy of Sciences
(1029471301).
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