Applied Clay Science 109–110 (2015) 22–32

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Applied Clay Science

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

Research paper

Determination of adsorptive properties of expanded vermiculite for the

removal of C. I. Basic Red 9 from aqueous solution: Kinetic, isotherm and
thermodynamic studies
Osman Duman ⁎, Sibel Tunç, Tülin Gürkan Polat
Akdeniz University, Faculty of Science, Department of Chemistry, 07058 Antalya, Turkey

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

Article history: The adsorption characteristics of toxic Basic Red 9 (BR9) onto expanded vermiculite were determined. The effect
Received 16 December 2014 of contact time, initial dye concentration, pH and temperature on the adsorption process was investigated. The
Received in revised form 4 March 2015 adsorption amount of BR9 onto expanded vermiculite increased with increasing initial dye concentration and
Accepted 5 March 2015
pH, but it displayed a decrease with increasing temperature. The adsorption kinetics of BR9 followed the pseudo
Available online 25 March 2015
second-order model. Freundlich model provided the best fitting with the experimental adsorption isotherm data
Keywords:
obtained at 25, 35 and 45 °C. Thermodynamic parameters indicated that the adsorption process was exothermic,
Dye removal occurred spontaneously and led to an increase in the randomness at the solid/solution interface. The desorption
Basic Red 9 of dye from spent adsorbent was investigated in water, ethyl alcohol and benzyl alcohol. The sign of the zeta po-
Vermiculite tential value of clay changed from negative to positive due to the adsorption of BR9 onto expanded vermiculite.
Kinetics The adsorption of BR9 led to some changes in the FTIR spectrum of adsorbent material. The maximum adsorption
Isotherm capacity of expanded vermiculite for BR9 adsorption is comparable with other adsorbents reported in the litera-
Thermodynamic ture. Therefore, expanded vermiculite as an efficient and economical adsorbent may be used for the removal of
dyes from wastewaters.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Several traditional methods including coagulation, flocculation,
ozonation, membrane-filtration, ion-exchange, oxidation and chemical
precipitation are known for the treatment of dye-containing effluents.
On the other hand, these techniques have some disadvantages such as
inefficiency at lower concentration, high energy and chemical reagents
requirement, generation of toxic sludge or other wastes as byproduct
that need careful treatment and disposal, high capital and operational
costs, etc. (Roy et al., 2012). In addition, it is difficult to remove the
dyes from wastewaters by biological treatment methods, because
many dyes used in the textile industry are stable to light and oxidizing
agents and resistant to aerobic digestion (Choi and Cho, 1996).
Adsorption technique is effective and practical in the treatment of
wastewaters containing dyes owing to its high efficiency, simplicity
and the availability of many adsorbents. The most used adsorbent to re-
move the dyes from aqueous solutions is activated carbon. On the other
hand, the application of activated carbon for a large-scale wastewater
treatment is limited because of its high cost. Therefore, instead of
⁎ Corresponding author. Tel.: +90 242 3102303; fax: +90 242 2278911.
E-mail addresses: osmanduman@akdeniz.edu.tr (O. Duman), stunc@akdeniz.edu.tr
(S. Tunç).
activated carbon, new adsorbents with low cost and high adsorption ef-
ficiency should be provided (Yu et al., 2010).
Vermiculite, a clay mineral with a porous structure, is a potential
candidate as an adsorbent material (Yu et al., 2010; Wen et al., 2013).
It is very abundant and much cheaper in comparison with other clays
such as montmorillonite, hectorite and saponite (Xu et al., 2003). It is
an expandable 2:1 mineral and often forms from alteration of mica
(Howe-Grant, 1992; Aristov et al., 2000). The structure of vermiculite
is shown in Fig. S1 (Supporting Information). Its crystal lattice consists
of one octahedral sheet sandwiched between two opposing tetrahedral
sheets. Tetrahedral sheets are composed of corner-linked tetrahedral,
whose central ions are Si4+ or Al3+. The octahedral sheet is composed
of edge-shared octahedra with Mg2+, Al3+ or Fe2+. Due to isomorphic
substitutions which are Al3+ for Si4+ substitution in tetrahedral sheets
and Mg2+ or Fe2+ for Al3+ substitution in octahedral sheets, vermicu-
lite layers have permanent negative charges. These charges are com-
pensated by the cations in the interlayer space (Tvardovski et al.,
1994; Poyato et al., 2002; Osman, 2006; Abollino et al., 2008).
The use of vermiculite as an adsorbent has been studied for the re-
moval of Hg(II) (Do Nascimento and Masini, 2014), Cr(III) (Badawy
et al., 2010; Sis and Uysal, 2014), Cu(II) (Badawy et al., 2010), Pb(II)
(Hongo et al., 2012; Sis and Uysal, 2014), Zn(II) (Sis and Uysal, 2014),
Cs (Suzuki et al., 2013), Ag(I) (Sari and Tüzen, 2013), Cr(VI) (Dultz
et al., 2012), Cd(II) (Panuccio et al., 2009), mineral and canola oils

http://dx.doi.org/10.1016/j.clay.2015.03.003
0169-1317/© 2015 Elsevier B.V. All rights reserved.
 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32
(Mysore et al., 2005), phthalate (Wen et al., 2013), basic cationic dye
(Choi and Cho, 1996), herbicides 2,4-D, diuron, alachlor, metolachlor
and triazine (de Rezende et al., 2011), dibenzothiophene (Froehner
et al., 2010), benzodiazepine (Carvalho et al., 2014) and cationic surfac-
tant cetylpyridinium chloride (Tarasevich et al., 2013) from aqueous so-
lution. Although there are many works published about the adsorption
of metal ions and organic compounds onto vermiculite, only one study
has been carried out to determine the dye adsorption properties of
vermiculite.
When pristine vermiculite flakes are strongly heated at high tem-
perature for a short time, expanded vermiculite is obtained (Zhang
et al., 2012a). If a heating process is applied to a vermiculite particle
rapidly above about 200 °C, the interlayer water in vermiculite turns
into steam. The pressure of the steam forces the silicate layers to
separate forming packets. This exfoliation creates a 10 to 20 times
volume expansion, but the basal dimensions of the particles are un-
changed (Kehal et al., 2010). Expanded vermiculite has a hydrophilic
nature and contains slit shaped pores (De Araujo Medeiros et al.,
2010). Expanded vermiculite is commonly used in industrial and ag-
ricultural applications due to its very low density, high absorption
capacity and excellent acoustical and thermal insulation properties
(Kehal et al., 2010).
On the other hand, only limited research has been performed on the
adsorptive properties of expanded vermiculite. Nishikawa et al. (2012)
investigated the removal of zinc ions by adsorption onto expanded
vermiculite. They reported that Zn(II) adsorption isotherm data were
fitted well with the Freundlich model and the adsorption process was
spontaneous, favorable and endothermic. The adsorption of cadmium
ions onto expanded vermiculite was studied by Mathialagan and
Viraraghavan (2003). In this study, optimum pH value for the adsorp-
tion of Cd(II) was found to be 6 and equilibrium time was determined
as 4 h. Turan and Ozgonenel (2013) investigated the adsorbent behavior
of expanded vermiculite to remove the copper ions from industrial
leachate. They reported that the removal of Cu(II) was 96.87% at pH 8,
adsorbent dosage of 10 g/L and contact time of 10 min. On the other
hand, in the literature, there are no reports about dye adsorption onto
expanded vermiculite.
Triarylmethane dyes form an important commercial dye class.
Triamino derivatives of triphenylmethane have the largest dye group
among the triarylmethane dye classes and the first member of this
group is C.I. Basic Red 9 (BR9) (Duman et al., 2011). BR9 is used com-
monly to color the products in textile, leather, paper and ink industries.
The discharge of BR9 from these industries into natural streams can
cause serious problems. BR9 is toxic and carcinogenic and has poor bio-
degradation (Huang et al., 2012). Therefore, wastewaters containing
dangerous dyes require treatment before being released into the envi-
ronment (Prola et al., 2013). In this study, the use of expanded vermic-
ulite was investigated for the removal of BR9 as a model dye from
aqueous solutions.
The aims of this study were to evaluate the adsorption efficiency of
expanded vermiculite as an adsorbent for the removal of toxic Basic
Red 9 (BR9) dye from aqueous solution, to investigate the effect of
contact time, initial dye concentration, pH and temperature on the ad-
sorption process, to determine the fitting of adsorption kinetics and iso-
therm data with various models, to calculate the thermodynamic
parameters and to understand the interactions between adsorbent
material and dye molecule by zeta potential and FTIR analyses.
2. Materials and methods
2.1. Materials
Vermiculite was supplied from Shanghai (China). C.I. Basic Red 9
(BR9) was obtained from Sigma-Aldrich (Germany). The chemical
structure of BR9 is shown in Fig. 1. Hydrochloric acid and sodium
23
Fig. 1. Chemical structure of C.I. Basic Red 9 (BR9).
hydroxide were purchased from Merck (Germany). All other chemicals
were reagent grade. Deionized water was used in the experiments.
2.2. Preparation and purification of expanded vermiculite
To prepare expanded vermiculite, vermiculite sample was placed in
a furnace heated to 500 °C. Then, the sample was kept at this tempera-
ture for 1–2 s and taken out of the furnace. The obtained sample was
labeled as expanded vermiculite.
After the expanded vermiculite was prepared, it was purified ac-
cording to the procedure described previously (Duman and Tunç,
2008). Briefly, in this procedure, a suspension was obtained by adding
of 100 g clay sample into 1 L deionized water. This suspension was
stirred at 960 rpm for 24 h by Variomag Poly model magnetic stirrer
and filtered through filter paper. Purified vermiculite was dried at
110 °C for 24 h. Dried samples were blended using a Waring Commer-
cial Blendor for 5 min at high speed. Afterwards, clay sample was sieved
by 100 μm sieve. The particles under 100 μm were used in the further
experiments.
2.3. Characterization of expanded vermiculite
X-ray diffraction (XRD) analysis of expanded vermiculite was per-
formed using a Shimadzu XRD-6000 model diffractometer with Cu Kα
tube (λ = 1.5406 Å, 40 kV, 30 mA) in the 2 theta range of 2 to 70° at
scanning rate 2°/min. For XRD measurements, divergence and scatter
slits are 1° and the width of receiving slit is 0.3 mm. Chemical composi-
tions of vermiculite and expanded vermiculite were determined by
using X-ray fluorescence (XRF) spectrometry. Powdered samples were
pressed and analyzed by a Philips PW2404 X-ray fluorescence (XRF)
spectrometer equipped with a rhodium X-ray tube, a maximum
power of 3600 W and flow and scintillation detectors. Samples were an-
alyzed at 60 kV and 125 mA. The chemical compositions of investigated
samples were determined using IQ + software. The cation exchange
capacity (CEC) and the density values of vermiculite and expanded
vermiculite were determined by ammonium acetate method and
picnometric method, respectively. Scanning electron microscope
(SEM) study was conducted at 15 kV using a Zeiss Leo-1430 model
scanning electron microscope to analyze the morphology of vermiculite
and expanded vermiculite. Before SEM analysis, the samples were coat-
ed with gold. The specific surface area value of expanded vermiculite
was obtained from N2 adsorption isotherm by a Quantachrome
Autosorb-1-C/MS surface area analyzer. Prior to N2 adsorption isotherm
experiments, vermiculite and expanded vermiculite were degassed at
130 °C (up to 10−6 Torr) for 12 h. The specific surface areas of samples
were calculated from the N2 adsorption isotherm data by Brunauer–
Emmett–Teller (BET) method, using relative pressure (P/P0) ≤ 0.26
24 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32
(Brunauer et al., 1938). FTIR analysis was carried out to see the changes
in the FTIR spectrum of vermiculite before and after BR9 adsorption. The
FTIR spectra of vermiculite samples were recorded by KBr pellet tech-
nique. The concentration of vermiculite in KBr is 1% (w/w). A Bruker-
Tensor 27 model FTIR spectrometer was used to obtain the IR spectra
of samples in the range of 400–4000 cm−1 at a resolution of 2 cm−1.
In FTIR analysis, 50 scans were accumulated.
2.4. Adsorption experiments
A stock solution of BR9 (1 × 10−4 mol·L−1) was prepared in deion-
ized water. The desired concentrations of dye solution were obtained by
diluting the stock BR9 solution in accurate proportions to obtain differ-
ent initial dye concentrations.
The batch adsorption technique was used to obtain the kinetic
and isotherm data. After the temperature of dye solutions (50 mL)
containing different concentrations of BR9 in Erlenmeyer flasks
reached the desired temperature value in Nüve ST 402 shaking
water-bath, accurately weighed quantities of expanded vermiculite
(0.1 g) were added to these flasks. After the Erlenmeyer flasks were
sealed, they were shaken at a constant shaking speed of 150 rpm.
At certain time intervals, the dye solutions were separated from ad-
sorbent by centrifugation at 10,000 rpm for 5 min. Preliminary ex-
periments showed that the effect of separation time on the amount
of adsorbed dye by expanded vermiculite was negligible. The absor-
bance values of dye solutions in the supernatant solutions were mea-
sured using a Cary 100 UV–visible spectrophotometer by monitoring
the absorbance changes at a wavelength of maximum absorbance
(540 nm). Then, the absorbance data were converted into concentra-
tion data using calibration relation pre-determined at 540 nm for
BR9. The amount of adsorbed dye per gram adsorbent at time t, qt
(mol·g− 1), was calculated by
ðC0 −Ct ÞV
qt ¼ ð1Þ
W and shaked at 25 °C for 3 h. The desorbed BR9 concentrations were
where C0 and Ct are the concentration of dye at time 0 and time t, re-
spectively (mol·L− 1), V is the volume of solution (L) and W is the
mass of adsorbent (g). The amount of adsorbed BR9 per gram ex-
panded vermiculite at equilibrium, qe (mol·g− 1), was obtained by
ðC0 −Ce ÞV
qe ¼ ð2Þ
W
where Ce is the equilibrium concentration of BR9 (mol·L− 1). For the
adsorption isotherm studies, the equilibrium time was determined
from kinetic studies.
To investigate the effect of temperature on the adsorption process,
adsorption experiments were conducted at 25, 35 and 45 °C. The effect
of the initial pH value was determined by adjusting the pH value of BR9
solutions in the range of 3.3 to 9.0 by using 0.1 mol·L− 1 HCl or
0.1 mol·L−1 NaOH before the experiments. The pH values of solutions
were measured with a Jenway 3040 ion analyzer using combined
glass electrode, which was calibrated with standard buffer solutions be-
fore use. In addition, adsorption isotherm experiments for the adsorp-
tion of BR9 onto untreated expanded vermiculite and untreated
vermiculite were carried out at 25 °C. All adsorption experiments
were repeated two times and reproducible within 4% error at most.
Mean values are reported in this study.
2.5. Zeta potential measurements
To determine the change in the surface charge of clay particles with
the adsorption of BR9 onto the expanded vermiculite, zeta potential
measurements were carried out by a Nano-ZS model (Malvern) Zetasizer
instrument which works with the technique of laser doppler electro-
phoresis (4 mW He–Ne, 633 nm). Electrophoretic mobilities (UE) of
particles were measured by the instrument and then automatically con-
verted to zeta potential by employing the Smoluchowski equation
(Eq. (3));
4πη
Zeta potential ¼ UE ð3Þ
ε
where η is the viscosity of suspending liquid and ε is the dielectric con-
stant (Giese and Van Oss, 2002).
To investigate the effect of dye adsorption on the zeta potential value
of expanded vermiculite particles, a series of clay-BR9 suspension was
prepared by adding of 50 mL dye solutions at different concentrations
(40 × 10−6 mol·L−1–140 × 10−6 mol·L−1) into the Erlenmeyer flasks
containing 0.1 g clay sample. The suspensions were shaken in Nüve ST
402 shaking water bath at 150 rpm and 25 °C for 180 min. Then, the
zeta potential measurements of expanded vermiculite-dye suspensions
were carried out. The average of 15 measurements was used to repre-
sent the zeta potential data. The percentage difference in the measured
zeta potential values of suspensions was, on the average, less than 2% of
the mean of the 15 values.
2.6. Desorption studies
Desorption studies were carried out to determine the desorption ef-
ficiency of dye adsorbed by expanded vermiculite in the presence of
water, ethyl alcohol or benzyl alcohol. Firstly, expanded vermiculite
was loaded with dye. To load the BR9 onto clay, 0.1 g expanded vermic-
ulite samples were shaken in Erlenmeyer flasks at a constant shaking
speed of 150 rpm and 25 °C for 3 h with 50 mL 100 × 10−6 mol·L−1
BR9. Then, dye loaded vermiculites were centrifuged at 10,000 rpm for
5 min by a Hettich Universal II model centrifuge and dried at room tem-
perature for 72 h. In order to test the dye desorption from adsorbent,
BR9 loaded expanded vermiculite samples were added to Erlenmeyer
flasks containing 50 mL deionized water, ethyl alcohol or benzyl alcohol
measured spectrophotometrically. The amount of dye desorption from
expanded vermiculite was calculated by Eq. (4)
qeðdesorptionÞ
Desorptionð%Þ ¼  100 ð4Þ
qeðadsorptionÞ
where qe(desorption) and qe(adsorption) are the amount of dye desorbed
from adsorbent and the amount of dye adsorbed onto adsorbent,
respectively.
3. Results and discussion
3.1. Characterization of expanded vermiculite
The XRD pattern of expanded vermiculite is shown in Fig. 2A. The re-
sults of XRD analysis indicated that sample consisted of mainly vermicu-
lite and small amounts of mica, illite and hydrobiotite. The chemical
composition of expanded vermiculite obtained from XRF analysis is
given in Table S1 (Supporting Information). The chemical compositions
of vermiculite and expanded vermiculite are similar. These samples
have essentially Si4+, Mg2+, Al3+, Fe3+ and K+. The CEC values were de-
termined to be 0.560 meq·(g vermiculite)−1 and 0.568 meq·(g expanded
vermiculite)−1. The CEC value is almost the same for vermiculite and ex-
panded vermiculite. The density values of vermiculite and expanded ver-
miculite are 2.894 g·cm−3 and 0.400 g·cm−3, respectively. After the
pristine vermiculite was kept at high temperature of 500 °C for 1–2 s,
the density of expanded vermiculite decreased approximately 7 fold.
SEM pictures of vermiculite and expanded vermiculite are illustrated in
Fig. 2B. The expanded vermiculite was more voluminous than vermiculite
due to the vaporization of water from interlayer of vermiculite during the
preparation of expanded vermiculite. The nitrogen adsorption isotherm
 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32 25

600

Intensity (CPS)
450
V
I V
300 V
V
HB V
HB
150 V

(A)
0
0 10 20 30 40 50 60 70

2 Theta (°)

(a) 2 __
µm 2 __
µm
(b)

(B) (B)

30
Adsorbed volume (cm .g )

Pore size distribution (cm .Å .g )

0.0010
-1
-1

-1

24 0.0008
3
3

0.0006

0.0004
18
0.0002

0.0000

12 0 20 40 60 80 100

Pore diameter (Å)

6
(C)
0
0.00 0.20 0.40 0.60 0.80 1.00
Relative pressure (P/P0)

Fig. 2. (A) XRD pattern of expanded vermiculite (V: Vermiculite, M: Mica, I: Illite, HB: Hydrobiotite), (B) SEM pictures of vermiculite (a) and expanded vermiculite (b) and (C) Nitrogen
adsorption isotherm of expanded vermiculite (Inset shows the pore size distribution of clay according to BJH theory).

data given in Fig. 2C were used to calculate the specific surface area of ex- in Fig. 2C (inset). This graph indicates that expanded vermiculite consists
panded vermiculite. The BET specific surface area was calculated to be of pores mainly with mesopore character. The total pore volume of adsor-
7.8 m2·g−1 for vermiculite and 9.8 m2·g−1 for expanded vermiculite by bent is 0.0043 cm3·g−1.
multipoint BET method. This result can be explained with the increase
in pore volume or the decrease in density of expanded vermiculite due 3.2. The effect of contact time and initial dye concentration
to vaporization of water from interlayer and increased separation of the
silicate layers. BET specific surface area values of vermiculite and expand- The adsorption of BR9 from aqueous solution by expanded vermicu-
ed vermiculite are in agreement with literature values. Perez-Maqueda lite as a function of contact time is shown in Fig. 3A. The amount
et al. (2003) have reported a BET specific surface area of 7 m2·g−1 for nat- adsorbed dye by expanded vermiculite was very high in the first
ural Mg2+-vermiculite. The BET specific surface area of expanded vermic- 10 min owing to the presence of large amount of adsorption sites on
ulite was found to be 9 m2·g−1 by Aristov et al. (2000) and 9.8 m2·g−1 by the adsorbent for the removal of dye. After 10 min, adsorption slightly
Huang et al. (2014). The pore size distribution graph obtained according increased with the increase in contact time until 25 min. After 25 min,
to Barrett–Joyner–Halenda (BJH) theory (Barrett et al., 1951) is shown there was no significant change in the adsorption amount of dye.
26 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32

equilibrium time required for BR9 adsorption by vermiculite is relative-

qt (10 mol BR9/g vermiculite)

5.0 (A)
ly shorter than other adsorbent materials.
The adsorption amount of BR9 is significantly affected by the initial dye
4.0
concentration (Fig. 3A). As the initial BR9 concentration is increased from
40.0 × 10−6 mol·L−1 to 100 × 10−6 mol·L−1, the adsorption amount on
3.0 the expanded vermiculite increased from 1.84 × 10−5 mol·g−1 to
4.19 × 10−5 mol·g−1 at contact time of 240 min.
2.0
3.3. Adsorption kinetics
40.0x10 -6 mol.L-1 BR9
-5

1.0 60.0x10 -6 mol.L-1 BR9

80.0x10 -6 mol.L-1 BR9 The investigation of adsorption kinetics provides very useful infor-
100x10 -6 mol.L-1 BR9
0.0
mation in the design of adsorption systems. In this study, several kinetic
0 50 100 150 200 250
models including pseudo first-order, pseudo second-order, Elovich and
intra-particle diffusion were used to understand the kinetic behavior of
t (min)
adsorbent in the adsorption process. Pseudo first-order rate equation is
3.6 expressed as (Lagergren, 1898)
qe (10 mol BR9/g vermiculite)

(B)
ln ðqe −qt Þ ¼ ln qe −k1 t ð5Þ

3.5 where qe and qt are the amounts of BR9 adsorbed by adsorbent

(mol·g−1) at equilibrium and time t (min), respectively, and k1 is the
pseudo first-order rate constant (min−1). Rate constant, k1, can be cal-
culated from the slope of the plot of ln(qe − qt) versus t.
3.4 Pseudo second-order model can be expressed by the following linear
equation (McKay et al., 1999)
-5

t 1 1
¼ þ t ð6Þ
3.3 qt k 2 qe 2 qe
2 4 6 8 10
pH where k2 is the pseudo second-order rate constant (g·mol−1·min−1).
Initial sorption rate (h) is equal to k2·q2e (mol·g−1·min−1). qe and k2
3.6
parameters can be determined from the slope and intercept values of
(C)
qt (10 mol BR9/g vermiculite)

the plot of t/qt versus t.

3.4 The linearized form of Elovich equation is given in Eq. (7) (Shek
et al., 2009):
3.2
1 1
qt ¼ ln ðαβÞ þ ln t ð7Þ
β β
3.0
where α (mol·g− 1·min− 1) and β are Elovich constants. These con-
stants can be calculated from the plot of qt versus ln t.
-5

2.8
2.6
0 50 100 150 200
t (min)
Fig. 3. (A) The effect of contact time on the adsorption of BR9 (initial dye concentrations:
40.0 × 10−6 mol·L−1–100 × 10−6 mol·L−1, T: 25 °C, pH: 6.8 and adsorbent dosage: 2 g/L),
(B) the effect of pH on the adsorption of BR9 (initial dye concentration:
80.0 × 10−6 mol·L−1, T: 25 °C, adsorbent dosage: 2 g/L and contact time: 180 min) and
(C) the effect of temperature on the adsorption of BR9 (initial dye concentration:
80.0 × 10−6 mol·L−1, pH: 6.8, adsorbent dosage: 2 g/L and contact time: 0–240 min).
Therefore, the necessary time to reach the equilibrium was 25 min. The
contact time was fixed as 180 min for all adsorption experiments, ex-
cept kinetic studies, to obtain reliable and consistent experimental
results. Contact time is one of the most important parameters for eco-
nomical wastewater treatment application and a short adsorption equi-
librium time favors the application of the adsorption process (Wang and
Chu, 2011). For the adsorption of BR9 onto various adsorbents, the
adsorption equilibrium time was determined to be 210 min for a
cellulose-based multicarboxyl adsorbent (Zhou et al., 2013), 550 min
for activated carbon (Kong et al., 2014), 105 min for bottom ash and
90 min for deoiled soya (Gupta et al., 2008). Compared with previous
studies about BR9 adsorption onto various adsorbents, the adsorption
25 °C
35 °C Intra-particle diffusion equation can be described as (Weber and
45 °C
Morris, 1963):
250 0:5
qt ¼ k i t ð8Þ
where ki is the intra-particle diffusion rate constant (mol·g−1·min−0.5).
The slope of the plot of qt versus t0.5 gives the rate constant, ki.
The values of pseudo first-order rate constant obtained from the
plots of ln(qe − qt) versus t are given in Table 1 together with the
regression coefficients. The regression coefficients for the pseudo first-
order kinetic model are lower than 0.7822. Therefore, the adsorption
kinetics of BR9 onto expanded vermiculite does not follow the pseudo
first-order kinetic model.
The plots of t/qt versus t for the adsorption of BR9 onto clay at differ-
ent initial dye concentrations give straight lines (Fig. 4). The obtained ki-
netic parameters for the pseudo second-order model are listed in Table 1.
The regression coefficients are higher than 0.9999. This result indicates
that the adsorption kinetics of BR9 follows the pseudo second-order ki-
netic model. The values of pseudo second-order rate constant and the ini-
tial sorption rate displayed a change with the initial dye concentration
and temperature. As the initial dye concentration was increased from
40.0 × 10−6 mol·L−1 to 100 × 10−6 mol·L−1, the pseudo second-order
rate constant value decreased from 271.2 × 103 g·mol−1·min−1 to
77.61 × 103 g·mol−1·min−1. In addition, k2 value increased with the in-
crease in the solution temperature. In brief, the initial sorption rate value
 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32 27

Table 1
Kinetic parameters and regression coefficients for the adsorption of BR9 onto expanded vermiculite at different dye concentrations and temperatures.

Initial dye concentration Pseudo first-order Pseudo second-order Elovich equation

(mol·L−1)
T k1 r k2 h r α β r
(°C) (10−2 min−1) (103 g·mol−1·min−1) (10−5 mol·g−1·min−1) (mol·g−1·min−1) (×106)

40.0 × 10−6 25 1.854 0.7050 271.2 9.171 0.9999 1.423 × 1090 12.45 0.6621
60.0 × 10−6 25 0.8775 0.4910 144.8 10.12 0.9999 1.513 × 1024 2.847 0.8446
80.0 × 10−6 25 0.4112 0.6949 94.76 10.97 0.9999 4.769 × 1061 4.782 0.8455
100 × 10−6 25 0.8897 0.3202 77.61 13.71 1.000 6.844 × 1010 1.033 0.7941
80.0 × 10−6 25 0.4112 0.6949 94.76 10.97 0.9999 4.769 × 1061 4.782 0.8455
80.0 × 10−6 35 1.993 0.7822 102.4 11.28 0.9999 2.969 × 1031 2.778 0.8600
80.0 × 10−6 45 1.347 0.5883 151.6 15.80 1.000 4.545 × 1049 4.167 0.8736

exhibited an increase with the increase of initial dye concentration and
temperature.
The parameters of the Elovich model were calculated by applying
of linear regression analysis to qt versus ln t data. The obtained pa-
rameters are given in Table 1. For the Elovich equation, the regres-
sion coefficients are in the range of 0.6621 to 0.8736. This means
that the fitting of experimental kinetics data to the Elovich model is
not good.
Finally, the adsorption kinetic data were analyzed with the intra-
particle diffusion model. According to this model, the plots of qt ver-
sus t0.5 must pass through the origin and yield straight lines. On the
other hand, the obtained plots of qt versus t0.5 were not linear over
the whole time range. Therefore, intra-particle diffusion model is in-
appropriate to predict the adsorption kinetics of BR9 onto expanded
vermiculite over the whole range of process. This means that intra-
particle diffusion is not the rate-limiting step in the adsorption
process.
The magnitude of the activation energy (Ea) is useful in the determi-
nation of adsorption type. To calculate the activation energy of adsorp-
tion, pseudo second-order rate constant (k2) can be used in the
Arrhenius equation:
3.4. The effect of pH
The pH value of solution can affect the surface charge of clay particles
and sometimes the structure of dye molecules. Therefore, the pH value
of a solution is an important factor in the adsorption studies. The influ-
ence of initial pH value of dye solution on the BR9 adsorption amount by
vermiculite at a reaction time of 180 min is shown in Fig. 3B. The adsorp-
tion amount of expanded vermiculite increased moderately with the in-
crease in the pH value. This result can be explained by the surface
charges of the adsorbate and adsorbent. In a previous study by Duman
and Tunç (2008), the isoelectric point (pHIEP) of expanded vermiculite
was determined to be 2.57 by the zeta potential measurements. The
electrical charge at the clay surface/aqueous phase on protonation or
deprotonation of the surface hydroxyl can be ascribed as (Alkan et al.,
2005)
ð10Þ
ð11Þ
and at the isoelectric point

E 1
lnk2 ¼ lnA− a
RT
where A is the Arrhenius constant, R is the universal gas constant
(8.314 J·mol−1·K−1) and T is the temperature (K). The value of Ea for
the adsorption of BR9 by expanded vermiculite was calculated to be
18.40 kJ·mol− 1 from the plot of ln k2 versus 1/T (Fig. S2, Supporting
Information). Low activation energy (0–40 kJ·mol−1) indicates that
physical adsorption is effective in the removal of BR9 from aqueous
solution by expanded vermiculite (Hamoudi and Belkacemi, 2013).
ð12Þ
ð9Þ
where ░-S represents the surface of expanded vermiculite. It can be said
that the reaction in Eq. (10) and the reaction in Eq. (11) are responsible
for the surface charge of expanded vermiculite particles below the iso-
electric point and above the isoelectric point, respectively.
Expanded vermiculite has a negative surface charge above pHIEP. In
addition, BR9 had a positive charge in the studied pH range. Therefore,
when the pH value of solution was increased, a moderate increase oc-
curred in the adsorption amount of dye molecules due to the electro-
static interaction between expanded vermiculite and BR9.
3.5. The effect of temperature

40.0x10 -6 mol.L-1 BR9 The adsorption of BR9 onto vermiculite from aqueous solution at 25,
12 60.0x10 -6 mol.L-1 BR9 35 and 45 °C is illustrated in Fig. 3C. As the temperature of solution in-
80.0x10 -6 mol.L-1 BR9
t/qt (10 min.mol .g )
-1

100x10 -6 mol.L-1 BR9 creased from 25 °C to 45 °C, the adsorption amount of expanded vermic-
ulite showed a decrease from 3.40 × 10− 5 mol·g−1 to 3.23 ×
-1

9
10−5 mol·g−1. This result indicates that the adsorption process has an
exothermic nature and the BR9 adsorption onto the expanded vermicu-
6 lite is favored at lower temperatures.
6

3
3.6. Adsorption isotherms

Adsorption isotherms are extremely important in determining the

0 maximum adsorption capacity of an adsorbent, in understanding the
0 50 100 150 200 250 nature of adsorption process and in the adjustment of optimum adsor-
t (min) bent dosage in the adsorption process (Njoku et al., 2014). The adsorp-
tion isotherm curves of BR9 obtained at 25, 35 and 45 °C is shown in
Fig. 4. The fit of pseudo second-order kinetic model for the adsorption of BR9 onto Fig. 5A. In this study, Langmuir, Freundlich and Temkin isotherm models
expanded vermiculite at 25 °C. were used for the interpretation of experimental data. The linear forms
28 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32
qe (10 mol BR9/g vermiculite)
where qe is the amount of BR9 adsorbed by adsorbent at equilibrium
6 (A)
(mol·g−1), Ce is the equilibrium concentration of adsorbate
5 (mol·L−1), qmax is the maximum adsorption capacity at monolayer cov-
erage (mol·g−1), KL is the adsorption equilibrium constant related to
4 the energy of adsorption (L·mol−1), KF is a Freundlich constant
representing the adsorption capacity ((mol·g−1)(L·mol−1)1/n), n is a
2 constant depicting the adsorption intensity, K1 is the Temkin isotherm
energy constant (L·mol−1) and K2 is the Temkin isotherm constant.
-5

25 °C
1 The main difference among these isotherm models is in the variation
35 °C
45 °C
of heat of adsorption with the surface coverage. The Langmuir model as-
0 sumes uniformity, the Freundlich model assumes a logarithmic de-
0.0 0.8 1.6 2.4 3.2 4.0 crease and the Temkin model assumes a linear decrease in heat of
Ce (10-5 mol.L-1) adsorption with surface coverage (Ayranci and Duman, 2005).
The adsorption isotherm parameters obtained from the linear re-
gression analysis of Ce/qe versus Ce data for Langmuir model, ln qe ver-
qe (10 mol BR9/g adsorbent)

6.0 (B) sus ln Ce data for Freundlich model and qe versus ln Ce data for
Temkin model are given in Table 2 together with their corresponding
4.8 regression coefficients. The regression coefficients calculated from
Langmuir, Freundlich and Temkin isotherm models are very high
3.6 (r N 0.99) for all temperatures. Therefore, regression coefficients are
not decisive about which model represents the experimental data bet-
2.4 ter. These results are in agreement with the recent studies related to
the adsorption of phenolic compounds onto Starbon prepared from
-5

Expanded vermiculite
1.2 Raw expanded vermiculite starch and alginic acid polysaccharides (Parker et al., 2013) and the ad-
Raw vermiculite
sorption of Malachite Green onto rice husk activated carbon (Sharma,
0.0
2011). In addition, similar results were obtained for the adsorption of
0.0 1.0 2.0 3.0 4.0 5.0 6.0
some cationic surfactants, dyes and aromatic organic pollutants onto ac-
Ce (10-5 M)
tivated carbon cloth (Duman and Ayranci, 2006, 2010; Ayranci and
Duman, 2009, 2010). When the regression coefficients are insufficient,
Fig. 5. (A) Adsorption isotherms for the adsorption of BR9 onto expanded vermiculite in
the residual root mean square error (RMSE) and the composite fraction-
water at 25, 35 and 45 °C. (B) Adsorption isotherm parameters of Langmuir, Freundlich
and Temkin equations and error values for the adsorption of BR9 onto expanded vermic- al error (HYBRD) analyses can provide good results for the determina-
ulite, untreated expanded vermiculite and untreated vermiculite at 25 °C. Solid lines show tion of the best isotherm model representing the experimental data.
the Freundlich isotherm. (Dye concentrations: 30.0 × 10−6 mol·L−1– Mathematical expression of RMSE and HYBRD is given in Eqs. (16)
140 × 10−6 mol·L−1, pH: 6.8 and adsorbent dosage: 2 g/L).
and (17), respectively (Hadi et al., 2010; Tumsek and Avci, 2013);
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u n  2
of Langmuir, Freundlich and Temkin equations are given in Eqs. (13), u 1 X
(14) and (15), respectively (Smith, 1981; Allen et al., 2003): RMSE ¼ t q −qeðpredÞ ð16Þ
n−p i¼1 eð expÞ

Ce C 1 2
¼ e þ ð13Þ 2 3
qe qmax KL Xn q −q
6 eð expÞ eð pred Þ 7
HYBRD ¼ 4 5 ð17Þ
qeð expÞ
1 i¼1
lnqe ¼ ln K F þ ln Ce ð14Þ
n
where n is the number of experimental data, p is the number of param-
qe ¼ K1 ln K2 þ K1 ln Ce ð15Þ eters within the model equation, qe(exp) is the experimental qe at any Ce

Table 2
Adsorption isotherm parameters of Langmuir, Freundlich and Temkin equations and error values for the adsorption of BR9 onto expanded vermiculite at 25, 35 and 45 °C.

Langmuir parameters

T (°C) qmax (10−5 mol·g−1) KL (104 L·mol−1) r RMSE (10−6) HYBRD (10−7)

25 7.657 8.635 0.9910 1.968 8.032

35 7.232 8.011 0.9908 1.988 8.791
45 6.840 7.866 0.9959 1.340 4.907

Freundlich parameters

T (°C) KF (mol·g−1)·(L·mol−1)1/n 1/n r RMSE (10−6) HYBRD (10−7)

25 0.01761 0.5449 0.9933 1.536 6.741

35 0.01321 0.5284 0.9943 1.339 5.341
45 0.01041 0.5134 0.9961 1.515 4.834

Temkin parameters

T (°C) K1 (10−5 L·mol−1) K2 (105) r RMSE (10−6) HYBRD (10−7)

25 1.700 8.326 0.9912 2.153 10.09

35 1.603 7.761 0.9907 2.108 10.20
45 1.521 7.521 0.9940 1.621 8.309
 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32 29

and qe(pred) is the calculated qe value from isotherm model using the
best fitted parameters. The smaller RMSE and HYBRD values indicate
the better fitting of isotherm model to the experimental data.
The calculated RMSE and HYBRD values are given in Table 2. The
magnitude of RMSE and HYBRD values for the Freundlich model is
lower than those of Langmuir and Temkin models. Therefore,
Freundlich model fits best with the experimental isotherm data.
Freundlich constant, KF , representing the adsorption capacity de-
creased with the increase in the solution temperature. In other
words, an increase in temperature leads to a decrease in the adsorp-
tion capacity of expanded vermiculite. In addition, adsorption
process is favorable; because the values of 1/n are lower than 1
(Table 2).
Untreated vermiculite may also be a good adsorbent for the adsorp-
tion of BR9 from aqueous solution. Moreover, the preparation of ex-
panded vermiculite needs some energy. For practical applications, the
adsorption isotherm curves of BR9 adsorption onto untreated vermicu-
lite, untreated expanded vermiculite and expanded vermiculite should
be obtained to see the effect of exfoliation, washing, drying and blend-
ing processes on the maximum adsorption capacity of adsorbent. The
adsorption isotherm curves of BR9 adsorption onto expanded vermicu-
lite, untreated expanded vermiculite and untreated vermiculite obtain-
ed at 25 °C are presented in Fig. 5B. Adsorption isotherm parameters of
Langmuir, Freundlich and Temkin models were calculated and listed in
Table 3. For the adsorption of BR9 onto three adsorbents, the lowest
RMSE and HYBRD values were obtained for Freundlich model
(Table 3). This result indicates that Freundlich model has the best fitting
with the experimental isotherm data. The Freundlich constant, KF,
representing the adsorption capacity increases in the order untreated
vermiculite b untreated expanded vermiculite b expanded vermiculite
for the adsorption of BR9 dye. An increase in the specific surface area
of untreated vermiculite occurred after the exfoliation process. More-
over, the pores were more accessible after the blending process for the
dye molecules. The enhanced adsorption of BR9 is observed after the ex-
foliation, washing, drying and blending processes of untreated
vermiculite.
Although a direct comparison of BR9 adsorption capacity of vermic-
ulite with other adsorbents is difficult owing to different experimental
conditions and isotherm models, the maximum adsorption capacity
(qmax) is an important parameter. For the adsorption of BR9 onto ver-
miculite and various adsorbents used in literature, the qmax values
calculated from the Langmuir isotherm model are listed in Table 4. All
of the adsorbent materials have lower qmax value than vermiculite, ex-
cept activated carbon.
3.7. Thermodynamic parameters
The results obtained from adsorption isotherm study were used to
evaluate the thermodynamic parameters including Gibbs free energy
change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°). For
adsorbates with weak charge, the Langmuir equilibrium constant (KL)
can be used for the determination of ΔG° (Liu, 2009). The values of
ΔG° for the adsorption of BR9 onto expanded vermiculite can be calcu-
lated using the following equation,

ΔG ¼ −RT lnKL ð18Þ
where R is the gas constant (8.314 J·mol−1·K−1) and T is the absolute
temperature (K). ΔH° and ΔS° can be determined from van't Hoff equa-
tion:
ΔS0 ΔH 0 1
lnKL ¼ − : ð19Þ
R R T
ΔG° values were determined from Eq. (18). By using Eq. (19), ΔH°
and ΔS° values were calculated from the slope and intercept values of
the linear plot of ln KL versus 1/T (Fig. S3, Supporting Information).
The negative ΔG° value (−28.17 kJ·mol−1 at 25 °C) indicates that the
adsorption process is spontaneous thermodynamically. According to
the negative ΔH° value (− 3.70 kJ·mol−1), the adsorption process is
exothermic. The positive ΔS° value (82.01 J·mol− 1·K− 1) illustrates
the increase in randomness at the solid/liquid interface during the ad-
sorption process. Similar results were also reported for the adsorption
of C.I. Basic Yellow 87 onto aluminiferous MCM41 (commercial meso-
porous adsorbent) by Wu et al. (2012).
3.8. The effect of dye adsorption on the zeta potential of expanded
vermiculite
The variation of zeta potential value of expanded vermiculite with
the adsorption of BR9 having different initial dye concentration in the
range of 0 mol·L− 1 to 140 × 10− 6 mol·L− 1 is shown in Fig. 6. The

Table 3
Adsorption isotherm parameters of Langmuir, Freundlich and Temkin equations and error values for the adsorption of BR9 onto expanded vermiculite, raw expanded vermiculite and raw
vermiculite at 25 °C.

Langmuir parameters

Adsorbent qmax KL r RMSE HYBRD

(10−5 mol·g−1) (104 L·mol−1) (10−6) (10−7)

Expanded vermiculite 7.657 8.635 0.9910 1.968 8.032

Raw expanded vermiculite 6.890 5.345 0.9929 1.429 7.141
Raw vermiculite 6.016 4.211 0.9843 1.730 8.333

Freundlich parameters

T KF 1/n r RMSE HYBRD

(°C) (mol·g−1)·(L·mol−1)1/n (10−6) (10−7)

Expanded vermiculite 0.01761 0.5449 0.9933 1.536 6.741

Raw expanded vermiculite 0.01332 0.5524 0.9944 1.090 6.424
Raw vermiculite 0.007394 0.5219 0.9928 1.530 6.328

Temkin parameters

T K1 K2 r RMSE HYBRD
(°C) (10−5 L·mol−1) (105) (10−6) (10−7)

Expanded vermiculite 1.700 8.326 0.9912 2.153 10.09

Raw expanded vermiculite 1.543 5.036 0.9889 2.054 14.94
Raw vermiculite 1.312 4.350 0.9779 2.509 27.23
30 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32

Table 4
Comparison of the maximum adsorption capacity (qmax) values with literature data.

Adsorbent T (°C) pH qmax (mol·g−1) Reference

Fish bone 25 Natural pH 5.02 × 10−5 Kizilkaya (2012)

Bottom ash 30 9.0 2.12 × 10−5 Gupta et al. (2008)
Deoiled soya 30 9.0 3.99 × 10−5 Gupta et al. (2008)
Jalshakti® (starch based super absorbent polymer) 27 6.5 3.61 × 10−5 Dhodapkar et al. (2007)
Polyacrylamide/laponite nanocomposite hydrogel 30 7.5 7.34 × 10−5 Zhang et al. (2012b)
Activated carbon 32 8.0 44.8 × 10−5 Kumar and Sivanesan (2006)
Expanded vermiculite 25 6.8 7.66 × 10−5 This study

zeta potential value of expanded vermiculite-water suspension is
−37 mV in the absence of dye molecules. This means that the net sur-
face charge of the adsorbent is negative in water. The zeta potential
value of expanded vermiculite increased with the addition of BR9 into
the clay suspension. For the equilibrium dye concentrations of
1.64 × 10− 5 mol·L−1 and 1.89 × 10− 5 mol·L−1, the zeta potential
values of expanded vermiculite were measured to be − 3.77 mV and
+0.897 mV, respectively. These results indicate that the zeta potential
value of the clay particles changed from negative to positive with the
adsorption of dye molecules onto vermiculite. In the presence of
140 × 10−6 mol·L−1 BR9 (initial dye concentration), the zeta potential
value of vermiculite reached +5.37 mV. According to the results of zeta
potential measurements, hydrogen bonding and electrostatic interac-
tions may play an important role in the adsorption process. The dye
molecules can form hydrogen bonding with vermiculite. In addition,
dye dissolved in water has a positive charge on its “N” center. Therefore,
electrostatic interactions between negatively charged vermiculite parti-
cles and positively charged dye molecules may contribute to the adsorp-
tion process. Due to the formation of hydrogen bonding and the
electrostatic attraction forces, the negative charge of the original ver-
miculite is neutralized by the adsorption of positively charged BR9 mol-
ecules. After a certain amount of dye adsorption, the zeta potential of
vermiculite becomes positive owing to the adsorption of positively
charged BR9 molecules onto the particle surface of clay.
3.9. Desorption of BR9 from spent expanded vermiculite
Desorption studies can contribute to the understanding of the regen-
eration of adsorbent. In this study, water, ethyl alcohol and benzyl alco-
hol were used as the solvent to remove the dye from adsorbent. The
desorption amount of BR9 from expanded vermiculite in water, ethyl al-
cohol and benzyl alcohol is displayed in Fig. 7. In comparison with alco-
hols, the desorption amount in water is very low. A similar result was
reported for the desorption of quinoline from spent adsorbents, granu-
lar activated carbon and bagasse fly ash (Rameshraja et al., 2012). The
highest desorption amount was obtained with ethyl alcohol. This
10
0
Zeta potential (mV)
study shows that ethyl alcohol is a potential medium in the regenera-
tion of expanded vermiculite and the recovery of BR9.
3.10. FTIR study
FTIR spectra of expanded vermiculite before and after BR9 adsorp-
tion are illustrated in Fig. 8. In the FTIR spectrum of expanded vermicu-
lite, the O–H stretching vibration was observed at 3717 cm− 1 for
interlayer water molecules and at 3418 cm−1 for silanol groups. The
spectrum of expanded vermiculite showed a weak absorption at
1640 cm−1 representing the O–H bending vibration of water molecules.
A strong band observed at 996 cm−1 is related to the Si–O stretching vi-
bration. Two weak absorption peaks recorded at 820 cm−1 and
687 cm−1 are assigned to the bending vibrations of Al–OH and Al–O, re-
spectively. The Si–O–Mg bending vibration in expanded vermiculite
was observed at 456 cm−1 (Arab et al., 2002; Da Fonseca et al., 2006a,
2006b; Duman and Tunç, 2008).
The bands in the FTIR spectrum of pure BR9 (Fig. 8) represent the
stretching vibration of N–H at 3439 cm− 1 and 3307 cm− 1, the C–H
stretching of aromatic ring at 3186 cm−1, the bending vibration of N–
H at 1630 cm− 1, the stretching vibration of C–C in aromatic ring at
1585 cm− 1 and 1459 cm− 1, and the stretching vibration of C–N at
1369 cm−1. The in-plane C–H bending vibration appears at
1169 cm−1. The bands obtained at 907 cm−1 and 843 cm−1 are related
to out-of-plane C–H bending vibration. N–H wagging vibrations are ob-
served at 563 cm−1 and 508 cm−1.
Some changes can be observed between the FTIR spectra of expand-
ed vermiculite before and after BR9 adsorption. Compared with the FTIR
spectrum of pure expanded vermiculite, a shift from 3418 cm− 1 to
3405 cm−1 in the O–H stretching vibration of silanol groups of clay is
observed after the adsorption of BR9 onto the expanded vermiculite
(Özcan et al., 2006; Chen et al., 2007). In addition, the absorption band
corresponding to the N–H stretching vibration of BR9 was observed at
3405 cm−1. As a result of the attachment of BR9 onto the adsorbent, a
shift from 1369 cm− 1 to 1372 cm− 1 in the absorption peak of BR9
was observed after adsorption process. Additionally, the adsorption of
BR9 caused the shifts in the Al–O and Si–O–Mg bending vibrations of ex-
panded vermiculite to lower wavenumbers (685 cm−1 and 451 cm−1).
The results of FTIR study demonstrate that the silanol groups of

30

-10
24
% Desorption

-20
18

-30
12

-40 6
0.0 0.6 1.2 1.8 2.4 3.0

Ce (10-5 mol.L-1) 0
Water Ethyl alcohol Benzyl alcohol
Fig. 6. The change of zeta potential value of expanded vermiculite with the adsorption of
BR9 in water (the initial BR9 concentrations: 0 mol·L−1–140 × 10−6 mol·L−1, adsorbent Fig. 7. The desorption of BR9 from expanded vermiculite in water, ethyl alcohol and benzyl
dosage: 2 g/L, contact time: 180 min and T: 25 °C). alcohol at 25 °C.
 O. Duman et al. / Applied Clay Science 109–110 (2015) 22–32 31

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4. Conclusions
Kinetic, isotherm, thermodynamic and desorption studies were car-
ried out comprehensively for the adsorption of BR9 from aqueous solu-
tion onto expanded vermiculite. Experimental results showed that a
short contact time of 25 min was sufficient to reach the equilibrium.
The increase in the temperature of the solution exhibited a negative ef-
fect on the adsorption process. On the other hand, the increase in the
initial dye concentration and pH values caused an increase in the ad-
sorption amount. Among the studied kinetic models, the best fitting of
experimental data was obtained with the pseudo second-order kinetic
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values led to an increase in the initial sorption rates. Adsorption iso-
therm studies displayed that Freundlich isotherm model fitted well
with the experimental equilibrium data. As the temperature of solution
was increased, a decrease was observed in the adsorption capacity value
of expanded vermiculite. Negative ΔG° values reflected the spontaneous
nature of adsorption process. Exothermic nature of adsorption was re-
vealed from negative ΔH° value. Positive ΔS° value illustrated the in-
crease in the randomness at the adsorbent/solution interface. The zeta
potential value of expanded vermiculite was converted from negative
to positive due to the adsorption of BR9 onto expanded vermiculite.
For the spent expanded vermiculite, the highest desorption amount
was obtained by ethyl alcohol solution. FTIR analysis confirmed the ad-
sorption of BR9. This study showed that expanded vermiculite has a
high adsorption capacity and adsorption rate for the BR9 adsorption.
Therefore, it is a potential adsorbent candidate for the removal of dyes
from wastewaters.
Acknowledgments
Central Laboratory of Middle East Technical University and TUBITAK
are acknowledged for determining the some characterization properties
of clay sample.
Appendix A. Supplementary data
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