Journal of Environmental Chemical Engineering 4 (2016) 16421652

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Journal of Environmental Chemical Engineering

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

Physicochemical parameters of Hg(II) ions adsorption from aqueous

solution by sepiolite/poly(vinylimidazole)
Ali Karaa,* , Nalan Tekinb , Aysu Alana , Akif afaklb
a
b

Department of Chemistry, Uludag University, Bursa, Turkey

Department of Chemistry, Kocaeli University, Kocaeli, Turkey

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 4 August 2014
Received in revised form 15 February 2016
Accepted 23 February 2016
Available online 26 February 2016

The sepiolite/Poly(vinylimidazole) (sepiolite/PVI) composite was prepared by in situ polymerization of

vinyl imidazole (VIM) and sepiolite, which was not modied. Fourier Transform Infrared (FTIR) analysis,
X-ray diffraction (XRD) spectra, Scanning Electron Microscopy (SEM) images and Differential Scanning
Calorimetry (DSC) exhibited that sepiolite/PVI composite was successfully produced. The theoretical
maximum adsorption capacity was calculated to be 345.3 mg g
1 (concentration range of
1001000 mg L
1) in Hg(II) solution at pH 6.5 at 298 K. The adsorption kinetics and isotherms were
also investigated for the adsorption process. The adsorption isotherms data were well tted to the
Langmuir model for the adsorption of Hg(II) onto sepiolite/PVI. The thermodynamic parameters (DG ,
DH , and DS ) were calculated which the composite could be considered as a spontaneous, endothermic
and mainly physical adsorption process. The equilibrium parameter (RL) indicated that sepiolite/PVI
composite was useful for Hg(II) removal from aqueous solutions.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Sepiolite
Poly(vinylimidazole)
Hg(II) adsorption
Composite

1. Introduction
Hg(II) is potential carcinogenic and very toxic metal found in
various industrial wastewaters, which originate from electroplating, paint and battery manufacture and mining activities [1,2].
Exposure to Hg(II) leads to various disorders and diseases in the
body due to the toxic effects of these ions even at very low
concentrations [3,4]. Therefore, in order to minimize the harmful
effects of Hg(II), removal of mercury from waste waters is very
important before it poses a treat.
The conventional methods used to remove Hg(II) from wastewaters are chemical precipitation, reverse osmosis, coagulation,
ion-exchange and solvent extraction [2,5,6]. These methods are
costly and have disadvantages such as generation of toxic sludge,
incomplete metal removal and high energy requirements. Therefore, adsorption which is an alternative to these treatment
methods is considered to be an effective and economical method
for removal of Hg(II) from waste water [710]. Still, there is a need
for efcient and environmentally friendly systems for reducing Hg
(II) contamination. Therefore, developing an adsorbent with large
surface area and small diffusion resistance is important. Recently

* Corresponding author at: Grkle Campus, Nilfer, 16059 Bursa, Turkey. Fax:
+90 224 2941733.
E-mail address: akara@uludag.edu.tr (A. Kara).
http://dx.doi.org/10.1016/j.jece.2016.02.028
2213-3437/ 2016 Elsevier Ltd. All rights reserved.

the adsorption method using a polymer/clay composite adsorbent

has been applied to the removal of wastewater containing Hg(II)
owing to its convenience and simplicity [6,4,1113].
Nitrogen-rich polymers have been used for mercury adsorption
due to a high afnity of nitrogen to mercury [14,15]. Among these
polymers poly(vinylimidazole) (PVI) is a well-known polymer used
in studies because of relatively simple to synthesize and imidazole
groups of PVI have complexation properties with catalytic divalent
metallic ions [16], low cost, antimicrobial activity and biodegradability [17,18] and low cost. In a previous study [11], n-vinyl
imidazole copolymer beads were used for Hg(II) adsorption from
aqueous solutions.
In recent years, polymer/clay composites have attracted great
interest in adsorption process because they often indicate
remarkably improved physical and mechanical properties when
compared either to the polymer matrix (for example, polymers
have relatively low surface area) [19]. Clays are chosen for
polymeric composites due to large specic surface areas and
excellent chemical stability [20]. So far, most of the investigation
on nanocomposite including clay is mainly focused on montmorillonite with layered structure [17,18], whereas only a few works
involves sepiolite [19,2126]. Sepiolite has attained increasing
interest in recent years because it exhibits extraordinary performance on the ame resistance, barrier properties, mechanical
properties and thermal stability produced from its special

A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

Notation

Ce
C0
Ea
Efe
DG
DH
DS
qe
qt
qm
QL
KL
n
KF
QDR
KDR

RL
k1
k2
kR
ki
R2
t
T

Concentration of Hg(II) ions at equilibrium (mg L
1)

Initial concentration of Hg(II) ions in solution (mg L
1)
Activation energy of adsorption (kJ mol
1)
Free energy of adsorption (kJ mol
1)
Gibbs free energy of adsorption (J mol
1)
Isosteric enthalpy of adsorption (J mol
1)
Entropy change of the adsorption process (J mol
1 K
1)
The amount of Hg(II) ions adsorbed on the adsorbent at
equilibrium (mg g
1)
The amount of Hg(II) ions adsorbed on the adsorbent at
any time (mg g
1)
The maximum amount of Hg(II) ions adsorbed per unit
mass adsorbent (mg g
1)
The maximum amount of Hg(II) ions adsorbed per unit
mass adsorbent (mg g
1)
The Langmuir constant related to the afnity of binding
sites (mL mg
1)
The heterogenity factor
The Freundlich constant
The maximum amount of Hg(II) ions adsorbed per unit
mass adsorbent (mg g
1)
The Dubinin-Radushkevich constant (mol2 J
2)
The polanyi potential (J mol
1)
The dimensionless separation factor
The rate constant of pseudo rst-order adsorption
(min
1)
The rate constant of pseudo second-order adsorption
((g mg
1) min
1)
The rate constant for the modied Ritchies-secondorder model (min
1)
The intraparticle diffusion rate constant (mg g
1
min
0.5)
Linear regression coefcient
Time (min)
Temperature (K)

1643

enhance the interfacial interaction between polymer and sepiolite.

Therefore, good dispersion of sepiolite within the polymer matrix
leads to improve the thermal and mechanical properties of
polymers [17,18].
The physical mixing between sepiolite and polymers could
hardly achieve desired dispersion due to aggregation of sepiolite in
the polymer matrix. For this reason, surface organic modication
of sepiolite can increase its compatibility with polymers before
applying physical mixing [19,26]. Another approach is in situ
polymerization usually yields polymer/clay composites in which
the clay is well dispersed [17,3133]. Therefore, the method may
help to prevent aggregation of clay in the host matrix.
In this study, sepiolite/PVI composite was prepared by situ
polymerization. Sepiolite without any chemical treatment was
directly used for the preparation of the composite. The sepiolite/
PVI composite samples were characterized by X-ray diffraction
(XRD), fourier transform infrared spectroscopy (FTIR), scanning
electron microscope (SEM) and differential scanning calorimetry
(DSC). According to the results, our present study provided a good
dispersion of sepiolite in the polymer matrix and an improvement
on thermal properties of polymer. In the present study, a sepiolite/
PVI composite was also used to remove heavy metal Hg(II) from
aqueous solutions. The adsorption conditions of Hg(II) onto the
composite have been investigated and also the kinetics and
thermodynamics of the adsorption process were evaluated.
2. Experimental
2.1. Materials
The sepiolite samples were obtained from Akta Lleta Co.
(Eskiehir, Turkey). The chemical composition of the sepiolite
determined by XRF is 53.47% SiO2, 23.55% MgO, 0.71% CaO, 0.43%
NiO, 0.19% Al2O3 and 0.16% Fe2O3 and exhibited a 21.49 loss was
exhibited upon ignition. The specic surface area of the sepiolite
was 342 m2 g
1 [34] 1-vinyl imidazole (VIM) and azobisisobutyronitrile (AIBN) were purchased from Aldrich and Fluka, respectively. All other chemicals were of reagent grade and purchased
from Merck (Darmstadt, Germany).
2.2. Preparation of sepiolite/PVI composite

structure [27,28]. But, there is no report on sepiolite/PVI composite

for Hg adsorption yet.
Sepiolite is a phyllosilicate that contains a continuous twodimensional tetrahedral sheet and differs from other layer silicates
in that it lacks continuous octahedral sheets. The sepiolite has the
TOT layer-brous structure. This structure contains in fact fragments of TOT structures that extend along the axis [29,30]. The
presence of silanol groups (SiOH) at the edges of the tunnels arise
due to the discontinuity of the silica sheets. Because of the tunnels
in the structure, the specic surface area of sepiolite is up to
300m2 g
1. The presence of silanol groups (SiOH) can cause to

The sepiolite sample was ground and sieved 75 mm size

fraction. Then, it was dried at 105  C for 24 h and used for further
experiments. sepiolite/PVI composite was prepared by in situ
polymerization as follows. AIBN was crystallized in methanol
before use. 10 mL 1-vinylimidazole, 10 mL deionized water and
0.16 g AIBN and calculated sepiolite were mixed in the ask. The
prepared suspension was stirred strongly for 3 h in the ultrasonic
bath for good dispersion of sepiolite and then N,N0 -methylenebisacrylamide (0.2 g) was added in the mixture. The mixture was

placed in a water bath at 65 C under nitrogen atmosphere for

Scheme 1. Proposed the formation process of sepiolite/PVI composite.

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A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

200 min. After synthesis the composite was washed repeatedly

with an excess amount of deionized water. Clean composite was
dried in air and in vacuum and ground into the powder form. The
formation process of sepiolite/PVI composite was shown in
Scheme 1.
2.3. Characterization experiments of the sepiolite/PVI composite
FTIR experiments were performed with a Bruker Tensor
27 spectrophotometer in the range of 4000400 cm
1, with a
2 cm
1 resolution over 30 scans, using Diamond ATR. XRD
experiments were recorded on a Rigaku Ultima IV X-ray
Diffractometer using copper K alpha (CuKa) radiation generated
at 40 kV, 30 mA and a scan speed of 1 /min. Morphologies of the
composite were examined by SEM-EDX (JOEL 50 A) microscope
operating at an accelerating voltage of 10 kV. The sepiolite and
fracture surface of composite were sputter-coated with gold before
observation. The thermal behavior of the materials was studied by
using a DSC (PerkinElmer DSC 4000) at 10  C min
1 heating rate
between room temperature and 400  C.
2.4. Adsorption experiments
All adsorption experiments were performed in erlenmeyer
asks on a magnetic stirrer at 200 rpm. 0.1 g of dried composite and
50 mL of 100 mg L
1 stock Hg(II) ions solution were used for the
adsorption experiments. The effect of pH on the adsorption of Hg
(II) ions onto sepiolite/PVI composite was investigated at different

pH values between 2 and 6.5. The optimum pH was then

determined as 6 and used further the adsorption experiments
which were carried out at 277, 298, 318, and 338 K. After the
adsorption was reached the equilibrium, the solutions were
centrifuged at 4500 rpm for 5 min and the supernatants were
separated and analyzed for metal ions by an UVvis spectrophotometer (Shimadzu-2100 UVvis, Japan). To evaluate the amount
of Hg(II) in the solution after adsorption process, 3 mL Hg(II)
solution was mixed with 0.1 mL 10
3 M 1,5-diphenyl carbazide as
the corresponding complexing agents and measured using UVvis
spectrophotometer at 555 nm. The absorbance values were plotted
against known concentration of six different metal ion solutions.
The correlation coefcient was 0.9946 and the absorbance was
linear between 25 mg L
1 and 300 mg L
1 (Fig. S1).
The equilibrium adsorption capacity was calculated using the
following equation:
V
qe C 0
C e
m

where, C0 and Ce are the initial and equilibrium concentration

(mg L
1) of Hg(II), qe (mg g
1) is the equilibrium adsorption
capacity, m (g) is the weight of the dried adsorbent and V (L) is the
volume of the Hg(II) solution.
The adsorption of Hg(II) ions onto sepiolite/PVI composite was
evaluated at constant temperatures of 277, 298, 318, and 338 K for
the Lagergren rst-order, pseudo-second-order, Ritchies-secondorder kinetic models and intraparticle diffusion model. The Hg(II)
solutions ranging from 100 to 300 mg L
1 were prepared and used

Fig. 1. FTIR spectra of (a) PVI, (b) sepiolite/PVI composite and (c) sepiolite.

A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

to evaluate the adsorption isotherms for the adsorption of Hg(II)

ions onto sepiolite/PVI composite.
3. Results and discussion
3.1. Characterization of the sepiyolit/PVI composite
The sepiolite/PVI composite was prepared by in situ polimerization of vinyl imidazole (VIM) and sepiolite, which was not
modied.
3.1.1. FTIR analysis
The FTIR spectra of sepiolite and sepiolite/PVI are presented in
Fig. 1. As shown in Fig. 1(c), a band at 1653 cm
1 due to the bending
of zeolitic water; bands in the 1200400 cm
1 range characteristic
of silicate; bands centered at 883 cm
1 due to symmetric
stretching vibrations of Si


O


Si groups of the tetrahedral sheet;

1645

bands at 1206 and 979 cm
1 due to Si

O bonds [35,36], and bands
at 685 and 642 cm
1 corresponding to MgOH bond vibrations
[24,37].
PVI showed adsorption bands at 3107 cm
1and 2952 cm
1associating with C
H (ring) and C


H (chain) stretching, respectively
(Fig. 1(a)). The adsorption bands obtained at 1495 cm
1,
908 cm
1and 818 cm
1 were ascribed to C


C and C


N stretching
of imidazole rings, respectively [38]. For sepiolite/PVI sample
(Fig. 1(b)), the absorption bands ascribed to the stretching
vibration of the CH in the ring of vinyl and CH2 in the chain
respectively shifted to 3110 and 2947 cm
1 [39]. The absorption
bands at 1415 and 1498 cm
1 were ascribed to bending vibration of
CH2 and the stretching vibration of the CC and CN group in PVI,
respectively (Fig. 1(a)) [40,41]. Characteristic absorption peaks in
the sepiolite/PVI spectra are approximately similar to the pure PVI
spectra. However, as can be seen from Fig. 1(b), the position of the
characteristic band intensities of sepiolite/PVI composite shift to

Fig. 2. XRD patterns of (a) sepiolite, (b) sepiolite/PVI composite and (c) PVI.

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A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

higher wave numbers compared to PVI peaks. In addition, the new

band appeared at 1014 cm
1 corresponds to the Si


O absorption
bond of sepiolite in the composite. After synthesis of the
composite, Si


O absorption bond at 979 cm
1 shifted to

1
1014 cm due to combined with PVIs bands. The characteristic
absorption peaks for both sepiolite and PVI were observed in the
FTIR spectrum of sepiolite/PVI (Fig. 1(b)) and the composite was
produced.
3.1.2. XRD analysis
The XRD patterns for sepiolite, PVI and sepiolite/PVI composite
were shown in Fig. 2. As shown in the gure, the intense diffraction
peak of sepiolite (110) (d-spacing = 1.268 nm) was found at about
2u = 6.966 , which corresponding to the internal channel reections [37]. Individual tetrahedral (T) octahedral tetrahedral (O)
(TOT) layers in sepiolite structure are strongly bonded by covalent
bonds which are different from the layers of smectite clays [42].
Therefore, even the completely exfoliated brous crystals of
sepiolite hardly have an effect on the location of the diffraction
peak (11 0) in the XRD pattern [43]. Compared with sepiolite, the
diffraction peak of sepiolite (11 0) was visible in the sepiolite/PVI
composite at 2u = 6.959 (Fig. 2b) with less intensity. Additionally,
some characteristic sepiolite peaks were disappeared in the
sepiolite/PVI composite. These results are considered as an
evidence for the homogenous dispersion of sepiolite in the
polymer matrix. The reason of good dispersion of sepiolite may
be in-situ synthesis of sepiolite/PVI composite [44].

Fig. 3, the thermal decomposition of PVI takes place in one major

step in the temperature range of 340500  C and the observation is
attributed to the decomposition of PVI chains [38,47,48]. The
maximum of the decomposition temperature according to the TGA
curve is determined at 450  C. It can be seen from Fig. 3 that
degradation of sepiolite/PVI composite (446  C) shifted to slightly
higher temperatures compared to PVI (442  C). The slightly
increase in the thermal stability of PVI may be due to that
sepiolite acts as a crosslinking agent retarded the motion of the
polymer chains [24].
3.1.4. SEM analysis
The SEM images of the sepiolite, PVI and sepiolite/PVI
composite are illustrated in Fig. 4. SEM images in Fig. 4(a) shows
that sepiolite has a brous or needle-like morphology and reveals
stone-like aggregation made up of lots of bers. It was also
observed that PVI showed spherical particulate structure and
consisted of particles with sizes <2 mm (Fig. 4(b)). Sepiolite/PVI
composite shows a dense and smooth surfaces and Fig. 4(c) reveals
that a good degree of dispersion of sepiolite in the polymer matrix.
It is also shown that the PVI covered the surface of sepiolite. For a
good adhesion between the sepiolite and the polymer matrix, this
result can be attributed to the high surface area of the sepiolite [49]
and strong hydrogen bonding between the PVI and silanol groups
of sepiolite [42]. The result of SEM analysis is consistent with that
of the XRD analysis.
3.2. Adsorption of Hg(II) ions from aqueous solutions

3.1.3. TGA analysis

Fig. 3(a,b) shows the thermogravimetric and the differential
thermogravimetric curves of PVI, sepiolite and sepiolite/PVI
composite. The thermogram of sepiolite showed a multi-step
dehydration process. The rst and major weight loss near 100  C
was ascribed to zeolitic water physically bonded to sepiolite on the
external surface and in the structural channels [45]. Sepiolite lost
two of the four coordinated crystallization water molecules at
about 300  C and the loss of the other two molecules occurred at
520  C [37,46]. The last step of the sepiolite weight losses
corresponded to the removal of constitution water or hydroxyl
groups around 750  C [37]. According to the data obtained from

3.2.1. Effect of initial concentration of Hg(II) ions on adsorption of Hg

(II) ions
The inuence of initial Hg(II) concentration on the adsorption of
Hg(II) by the sepiolite and sepiolite/PVI composite samples was
investigated to the effectiveness of sepiolite/PVI composite in
removing Hg(II) from aqueous solution. The initial concentration of
Hg(II) solution was varied from 100 to 1000 mg L
1. The amount of
mercury adsorbed for different initial concentrations onto sepiolite
and sepiolite/PVI was measured and the results are shown in Fig. 5.
The removal of mercury increased with an increase in the initial Hg
(II) concentration due to possibility of binding sites for the

Fig. 3. DSC curves of (a) PVI, (b) sepiolite/PVI composite and (c) sepiolite.

A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

1647

Fig. 4. SEM photographs of: (a) sepiolite, (b) PVI and (c) sepiolite/PVI composite.

adsorption of Hg(II) ions. Amount of metal adsorbed per unit mass

of adsorbent, qe is higher at high concentrations, as shown in Fig. 5.
A larger driving force for mass transfer at higher concentrations of
metal ions is responsible for the increase in loading capacity of the
adsorbent [2]. As concentration of metal ion increases, the
probability of surface adsorption increases because more ions

are available per unit surface area. The initial Hg(II) concentration
was selected as 300 mg L
1 for adsorption kinetic experiments and
investigation of temperature effect on adsorption while it was
1000 mg L
1 for pH experiment. Also, this study showed that the
adsorption capacity of sepiolite/PVI composite is higher in
comparison to that of sepiolite under the same conditions. By

Fig. 5. Effect of initial concentration on adsorption of Hg(II) ions onto sepiolite and sepiyolit/PVI composite (pH: 6.0; shaking rate: 200 rpm; dose of adsorbent: 0.1 g).

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A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

Fig. 6. Effect of pH on adsorption of Hg(II) ions onto the sepiyolit/PVI composite (pH: 6.0; shaking rate: 200 rpm; dose of adsorbent: 0.1 g; initial concentration of Hg(II) ions:
1000 mg L
1, temperature: 298 K).

formation of composite with PVI, the adsorption capacity of

sepiolite for Hg(II) was greatly enhanced.

tend to level off at pH 56.5, which was 612 mg g
1. Therefore, pH

6 was used in the following experiments.

3.2.2. Effect of pH on adsorption of Hg(II) ions

Heavy metal ion uptake capacity of adsorbents is affected by
solution pH. The pH of a solution affects metal species in solution
and the surface properties of the adsorbents [10]. Therefore, the
effect of pH on the Hg(II) adsorption was investigated at different
pH in the range of 26.5. The initial concentration of Hg(II) ions was
200 ppm and the adsorption capacity as a function of pH is shown
in Fig. 6. Sepiolite/PVI exhibited a low afnity for Hg(II) ions in
acidic conditions (pH < 5.0), and a higher afnity between pH
5.0 and 6.5. When the pH increased from 2 to 6, the decrease of the
concentration of H+ promoted the formation of the mercury
imidazole complex and increased the adsorption capacity of the
sepiolite/PVI composite [41]. With increasing pH, Hg(OH)+ and Hg
(OH)2 become the dominant species, which have higher afnity to
nitrogen-containing binding sites than that of Hg2+(aq) in acidic
solution [6]. The amount of Hg(II) adsorbed onto the composite

3.2.3. Effect of temperature on adsorption of Hg(II) ions

The effect of temperature on adsorption of Hg(II) ions by
sepiolite/PVI composite was investigated at a range of 277338 K. It
is found that adsorption capacity (qe) values increased from
65.04 to 288.10 (mg g
1) as T was increased from 277 to 338 K. This
change could be due to higher collision frequencies at higher
temperature and hence leading to more sorption [2]. The results of
the experiment are shown in Fig. 7.
3.3. Analysis of adsorption of Hg(II) ions from aqueous solutions
3.3.1. Analysis of adsorption kinetics
The kinetics experiments were carried out at different temperatures (277, 298, 318 and 338 K) in pH 6 and the initial
concentration of Hg (II) ions is 300 mg L
1. The results obtained
from kinetic studies are presented in Fig. SI 2ad. The values of the

Fig. 7. Effect of temperature on adsorption of Hg(II) ions onto the sepiyolit/PVI composite (pH: 6.0; shaking rate: 200 rpm; dose of adsorbent: 0.1 g; initial concentration of Hg
(II) ions: 300 mg L
1).

A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

1649

Table 1
Kinetic parameters for the adsorption of Hg(II) ions onto the sepiyolit/PVI composite.
Temperature Experimental
(K)
qe
(mg g
1)

277
298
318
338

65.04
131.8
286.3
288.1

Pseudo-rst-order kinetic
model

Pseudo-second-order kinetic model

Ritch-second order kinetic

Intraparticle diffusion
model

k1 103 qeq
R2
(min
1) (mg g
1)

h
k2  105
(mg (g min)
1) (g
(mg min)
1)

kR x 103 qeq
R2
(min
1) (mg g
1)

ki
R2
(mg g
1) min
0.5)

28.33
39.15
55.73
61.03

82.95
145.0
290.3
254.5

0.9488
1.313
0.9654
5.677
0.9022 22.34
0.9900 24.53

0.779
1.910
2.106
2.267

parameters and correlation coefcient obtained from these four

kinetic models (A description of the kinetic models is provided in
the Supporting material) are listed in Table 1. It can be seen from
Fig. SI 2b, the results show a good agreement with the pseudosecond-order kinetic model. The values of R2 for the pseudosecond-order kinetic model (Table 1) are very high, all greater than
0.9901, followed by those of the modied Ritchies-second-order
kinetic model (Fig. SI 2c), the pseudo-rst-order kinetic model
(Fig. SI 2a), and the intraparticle diffusion model (Fig. SI 2d),
respectively.
It was found that the values of the pseudo-second-order rate
constant, k2, increase from 0.779  10
4 to 2.267  10
4 (g (mg
min)
1) with increasing of the solution temperature from 277 to
338 K, respectively. A linear relationship between the k2 and
temperature was obtained by using the Arrhenius equation (the
equation is provided in the Supporting material) and it can be seen
from Fig. 8. The corresponding activation energy was determined
from the slope of the linear plot. From the Arrhenius equation, the
activation energy for adsorption, Ea, is 13.142 kJ mol
1 and the rate
constant for adsorption, k0, is 5.728  103 g mg
1 min.
The magnitude of determined activation energy explains the
type of sorption (physical or chemical). In physical adsorption, the
equilibrium is usually attained rapidly and easily reversible due to
small energy requirements. However, chemical adsorption is
specic and involves forces much stronger than physical adsorption. The range of 540 kJ mol
1 of activation energy correspond a

qeq
R2
(mg g
1)
129.9
172.4
325.7
328.9

0.9901 11.28
0.9907 29.55
0.9921 54.58
0.9904 53.15

119.0
181.8
357.1
370.4

0.9996
7.722
0.9803 12.98
0.9446 22.73
0.9429 23.11

0.9942
0.9440
0.8070
0.7740

physisorption mechanism or the range of 40800 kJ mol
1

suggests a chemisorption mechanism [50]. The value of the
activation energy in this study is 13.142 kJ mol
1 which indicating
that the adsorption is a physisorption.
3.4. Analysis of adsorption isotherm
Adsorption isotherm can be used for determine the adsorption
capacity of adsorbent and describe interaction of the adsorbate
interacts with adsorbent [51]. The Langmuir, Freundlich, and
DubininRadushkevich (DR) isotherm models (a description of
the isotherm models is provided in the Supporting material) were
used for the adsorption behaviors of Hg(II) onto sepiolite/PVI
composite.
The Langmuir and Freundlich constants and correlation
coefcients (R2) are given in Table 2. According to the correlation
coefcients, the equilibrium experiment data tted Langmuir
isotherm equation better than Freundlich isotherm equation. The
result indicates that the adsorption of Hg(II) ions onto sepiolite/PVI
adsorbent is a monolayer adsorption.
The dimensionless separation factors, RL (a description of RL is
provided in the Supporting material) obtained are listened in
Table 2. All the RL values for the adsorption of Hg(II) ions onto the
sepiolite/PVI composite are in the ranges 0.01410.8516 shows that
the adsorption process was favorable. Additionally, the equilibrium
isotherms can be well described by the Langmuir model. The

Fig. 8. The plots of ln k2 and ln KL versus 1/T for the determination of activation energy and thermodynamic parameters for adsorption of Hg(II) ions on the sepiyolit/PVI
composite.

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A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

Table 2
Parameters of Langmuir, Freundlich and DubininRaduskhevich isotherm models for the adsorption of Hg(II) ions onto the sepiyolit/PVI composite.
Temperature
(K)

277
298
318
338

Langmuir isotherm constants

Freundlich isotherm constants

DubininRaduskhevich isotherm constants

KL  104
(L mg
1)

QL
(mg g
1)

R2

RL

KF
(mg g
1)(L mg
1)1/n

R2

QDR
(mg g
1)

KDR  108
(mol2 J
2)

Efe
(kJ mol
1)

R2

1.742
4.024
62.67
555.6

227.3
345.3
480.8
69.77

0.9918
0.9902
0.9991
0.9996

0.36470.8516
0.19900.7131
0.01570.1376
0.01410.1254

4.698
7.242
98.16
101.0

1.573
1.787
3.551
3.137

0.9652
0.9722
0.6976
0.7896

728.5
1252.7
1218.1
1218.1

108.3

86.92

75.08

66.45

6.794
7.584
8.161
8.674

0.9933
0.9896
0.9861
0.9861

Scheme 2. Proposed adsorption mechanism between imidazole groups in sepiolite/PVI composite and Hg(II).

adsorption process is monolayer adsorption onto a surface with

nite number of identical sites, which are homogeneously
distributed over the adsorbent surface.
The Langmuir and Freundlich isotherm models do not give
information on the adsorption mechanism. Therefore, the equilibrium data obtained were tested with the DubininRadushkevich
isotherm model (DR isotherm). This isotherm model predicts the
nature of the adsorbate adsorption onto the adsorbent and is used
to calculate the mean free energy of adsorption.
The values of QDR and KDR were calculated and are shown in
Table 2. The mean free energy of adsorption (Efe) was calculated
from the KDR values using Eq. (2):
1
Efe p

2K D
R

The Efe value gives information about the adsorption mechanism

(physical or chemical). If it lies between 8 and 16 kJ mol
1, the
adsorption process occurs chemically. When an Efe value of
<8 kJ mol
1 indicates that the adsorption process proceeds
physically [52]. The calculated Efe values and other parameters
were summarized in Table 2. The results showed that the Efe values
for Hg(II) at 227 and 298 K were <8 kJ mol
1 and the values at
318 and 338 K were slightly higher than 8 kJ mol
1. The result
shows that the adsorption of Hg(II) onto sepiolite/PVI were mainly
by physical adsorptions. Therefore, we proposed the adsorption
mechanism between imidazole groups in sepiolite/PVI composite
and Hg(II) in Scheme 2. Similar mechanism for adsorption of Hg(II)
onto adsorbent included PVI was proposed in the literature
[41,53,54].

3.5. Analysis of adsorption thermodynamic

The vant Hoff equation shows to temperature dependence of
the equilibrium constant (K L ). Therefore, the equation can be used
to determine the thermodynamic parameters. The integrated form
of this equation is given as [55]:

 
DS DH 1


lnK L
3
R
R T
where T the absolute temperature (K), R is the gas constant


(J mol
1 K
1), DH and DS are the enthalpy and entropy changes of



the adsorption process. DH and DS can be determined from the

slope and intercept of the line obtained by plotting lnK L versus 1=T
(Fig. 8).

Table 3
DG , DH and DS values for the different solution temperatures used for Hg(II) ions
removal with the sepiyolit/PVI composite.
Solution temperature
(K)

DG

DH

DS

(kJ mol
1)

(kJ mol
1)

(J mol
1 K
1)

277
298
318
338

13.49

16.58

24.96

26.83

53.06

238.09

A. Kara et al. / Journal of Environmental Chemical Engineering 4 (2016) 16421652

1651

Table 4
The comparison of adsorption capacities of adsorbents for Hg(II).
Adsorbents

Temperature
(K)

Hg(II) initial concentration

(mg L
1)

pH

qm
(mg g
1)

Ref.

Bare Fe3O4
SH-Fe3O4-NMPs-0
SH-Fe3O4-NMPs-2
Nano-TiO2
PAM/ATP
SH-Fe3O4-NMPs-0.5
SH-Fe3O4-NMPs-1.5
SH-Fe3O4-NMPs-1
sepiolite/PVI
SS-g-VIM
CTS-3.0
CTS-2.0
CTS-1.0
PANI/HA
PANI/ATP

308
308
308
303
303
308
308
308
298
300
298
298
298
298
298

20500
20500
20500
100800
100900
20500
20500
20500
1001000
50500
250.742005.9
250.742005.9
250.742005.9
5300
10400

5
5
5
8
4.4
5
5
5
6
5
5
5
5
5
6

51.5
129.9
158.7
166.7
192.5
200.0
212.8
256.4
345.3
355.9
413.2
431.0
526.3
671
909.1

[57]
[57]
[57]
[2]
[58]
[57]
[57]
[57]
In this study
[41]
[1]
[1]
[1]
[6]
[4]

The equation of free energy for all studied temperature is

obtained as:


DG DH
T DS

From Eq. (4), the Gibbs free energy change of adsorption (DG) was
calculated as
13.49,
16.58,
24.96 and
26.83 kJ mol
1 for the
adsorption of Hg(II) ions onto the sepiolite/PVI composite at 277,
298, 318, and 338 K, respectively (Table 3). The negative DG values
indicated that the adsorption of Hg(II) ions onto the sepiolite/PVI
composite was thermodynamically feasible and spontaneous. The
change in free energy for physisorption is usually between
20 and
0 kJ mol
1, whereas that for chemisorption is often in the range of

80 to
400 kJ mol
1 [56]. The DG value obtained in this research
indicated that the adsorption is physisorption.

investigated and the thermodynamic parameters DG , DH and

DS were calculated. The results show a feasible, spontaneous and
endothermic adsorption process. The mechanism of adsorption
includes mainly electrostatic interactions (physical interactions)
between Hg(II) ions and sepiolite/PVI composite. So the adsorption
is a physisorption process. The comprehensive results suggested
that sepiolite/PVI composite has potential application for the
removal of Hg(II) from wastewater.
Acknowledgement
This work was partly supported by the Research Fund of the
University of Uludag Project Number: KUOP(F)-2013/29 and
Project Number: OUAP(F)-2012/28.

The enthalpy (DH ) and entropy (DS ) changes were determined as 53.06 kJ mol
1 and 238.9 J mol
1 K
1, respectively (Ta-

Appendix A. Supplementary data

ble 3), from lnK L versus 1/T plot (Fig. 10). The positive value of DH
conrmed that the adsorption process is endothermic in nature.


The positive values of DS also revealed the increase of randomness

at the solid-solute interface during the adsorption of Hg(II) ions
onto the sepiolite/PVI composite.
3.6. Comparison of some adsorbents on Hg(II) adsorption
A comparison between the adsorption capacities for removal of
the Hg(II) ions of sepiolite/PVI composite and other adsorbents
under similar conditions is presented in Table 4. From Table 4, it
can be seen that the maximum adsorption capacity of the sepiolite/
PVI composite is much higher than those of some composite
adsorbents reported in the literatures.
4. Conclusions
In this study, the sepiolite/PVI composite was prepared in situ
polymerization and used for the removal of Hg(II) in batch
experiments. The effects of the pH, initial Hg(II) concentration, and
temperature were investigated. The optimum pH value for Hg(II)
adsorption is found at pH 6. Equilibrium isotherm data were tted
using Langmuir, Freundlich, and DubininRaduskhevich (DR)
models. Among these models, Langmuir model is in good
agreement with the experimental data with high R2. The kinetic
parameters were evaluated utilizing the pseudo-rst-order,
pseudo-second-order, Ritchies-second-order, and the intraparticle diffusion kinetic models. The adsorption kinetics followed the
mechanism of the pseudo-second-order equation for all systems
studied. The adsorption of Hg(II) dependence on temperature was

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.jece.2016.02.028.
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