Applied Clay Science 43 (2009) 503–506

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Applied Clay Science

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Removal of the persistent pollutant chlorobenzene by adsorption

onto activated montmorillonite
R. Sennour, G. Mimane, A. Benghalem ⁎, S. Taleb
Laboratory of Materials Catalysis, Chemistry Department, Faculty of Sciences, Hai larbi Ben M'hidi BP 89 University of Sidi Bel - Abbes 22000, Algeria

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

Article history: The potential of activated bentonite was assessed for adsorption of chlorobenzene from aqueous solution.
Received 15 April 2008 The bentonite used was treated by chemical and thermal activation over 100–500 °C. The thermal activation
Received in revised form 12 June 2008 increased the adsorption capacity more strongly than chemical activation which consists to acid and
Accepted 22 June 2008
hydrogen peroxide treatment. The removal is dominated by adsorption at low initial concentrations and low
Available online 3 September 2008
temperatures and favourable in acidic media. The dependence of the adsorption on pH appears to be related
Keywords:
to the solubility of chlorobenzene. Thermodynamic parameters such as ΔH°, ΔS°, ΔG° and Ea have been
Adsorption calculated. The adsorption process is spontaneous and exothermic in nature. The Freundlich isotherm
Montmorillonite described the adsorption data over the concentration range (20–270 °C).
Chlorobenzene Crown Copyright © 2008 Published by Elsevier B.V. All rights reserved.
Thermal activation

1. Introduction activated bentonite for the removal of organic pollutants from water.
Chlorobenzene is used as a model component because it is formed by
The excessive and the uncontrolled use of fertilizers which are degradation of a number of aromatic pesticides, and it is highly toxic.
leached into surface and groundwater become a major problem.
Chlorobenzene is an organic compound used often in the production of 2. Materials and methods
pesticides and herbicides. It belongs to a group of ordinary con-
taminants of water. It causes an unpleasant taste and odour, even at 2.1. Adsorbent and adsorbate
low concentration (Environment Protection Agency, 1985). Clay
minerals are the most important natural adsorbent and have a The montmorillonite rich bentonite was collected at chemical Ltd,
privileged place in the purification of water (Bouras et al., 2002). Algerian Research Company “ENOF”. It was first sedimented to
Activated carbons are among the most effective commercial adsor-
bents, having specific high surface areas. Due to the relatively high cost
of activate carbons there have been attempts to utilize low cost, natural
adsorbents to remove traces of organic and inorganic contaminants
from wastewaters (Darwish et al., 1996). Several cheaper adsorbents
such as fly ash, silica gel, (Ahmed and Ram, 1992) and clay materials
have been applied for organic compound removal. Some studies (Boyd
et al., 1988; Brigatti et al., 1995; Gutierrez and Fuents, 1996) illustrate
the important need of clay materials treated by some chemical or
physical processes as adsorbents for removal of organic pollutants and
pesticides from water (Van den Heuvel and van Noort, 2004; Yapar
et al., 2005). The thermal activated clay is widely used as decolourant
to remove undesirable substances in oils (Siew et al., 1993) and red
sugar. The objective of this study is to evaluate the capability of

Abbreviations: MMA, thermal activated montmorillonite; MM, montmorillonite

(chemical activation).
⁎ Corresponding author. Tel./fax: +213 48 54 43 44; fax: +213 48 54 98 88.
E-mail address: Benghalem_has@yahoo.fr (A. Benghalem). Fig. 1. Solubility of chlorobenzene in water, λmax = 270 nm, T = 28 °C, pH = 7.1.

0169-1317/$ – see front matter. Crown Copyright © 2008 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2008.06.019
504 R. Sennour et al. / Applied Clay Science 43 (2009) 503–506

Table 1
Constants of Freundlich and Langmuir isotherms

Langmuir Freundlich
Sample Qmax K R2 KF 1/n R2
MM 3.28 1.57 0.96 39 0.84 0.98
MMA 174.8 2.39 0.97 197.2 0.58 0.98

components then saturated with sodium ion by stirring in a (1 N)

sodium chloride solution and used as such (named MM), its cationic
exchange capacity (CEC) was 110 meq/100gr, or after thermal activation
by heating to 773 K at 10 °C/min heating rate, in the air flow of 40 ml/min
(named MMA). The specific BET surface area was 110 m2/g (MM) and
250 m2/g (MMA) respectively. Chlorobenzene of analytical grade
obtained from Aldrich was used as received.

Fig. 2. Effect of initial concentration of chlorobenzene adsorption on MMA, µ = 500 rpm,
m = 0.5 g, pH = 7.1, T = 28 °C.
2.2. Characterization
The surface area was measured by adsorption of nitrogen
according to the BET-method on a Micrometrics 2000 apparatus.
Powder X-ray diffraction (XRD) analysis was carried out with a
Siemens D5000 diffractometer in the range of (0.99–40°) with slow
scan of 0.02°/min and with a diffracted beam-graphite monochro-
mator (Cu Kα1 radiation). Fourier transform infrared spectra FTIR were
measured with spectrophotometer Shimadzu Fourier Transform-8300
over the range (400–4599 cm− 1) using KBr pellet.

2.3. Adsorption test

Adsorption tests were carried out in a batch process by varying adsor-

Fig. 3. Effect of pH on the adsorption of chlorobenzene, µ = 500 rpm, C = 0.003 mol/L,
m = 0.5 g, T = 28 °C.
bent amount, initial concentration of chlorobenzene (1 and 5 mmol/L), at
pH 7. Known amounts of montmorillonite were dispersed in 100 ml
chlorobenzene solution. After equilibration, the dispersions were filtered
through a 0.2-µm syringe filter and analyzed. All experiments were
conducted in duplicate.
The equilibrium concentration of chlorobenzene was determined
spectrophotometrically (UV–Vis Spectrometer Lambder, type 2401 PC
fitted with a UV–Visible detectors set) at λmax = 270 nm.

eliminate quartz and cristobalite, by dispersing 100 g of bentonite in 3. Results and discussion
10 L of distilled water and collecting the supernatant dispersion of
particles b2 µm after the time (12 h), then treated with HCl (1 N) to To determine the maximum chlorobenzene concentration in
remove carbonates, and by hydrogen peroxide to remove organic water, solutions of various concentrations were prepared and their

Fig. 4. Infrared spectra of a chemical treated montmorillonite MM (b) and thermal activated montmorillonite MMA (a).
 R. Sennour et al. / Applied Clay Science 43 (2009) 503–506 505

Table 2
Thermodynamic values

ΔH(KJ/kmol) ΔS(KJ/kmol) ΔG (kJ/k mol) Constant K

289 K 308 K 318 K 338 K 289 K 308 K 318 K 338 K
MM −4.94 −0.0065 −3 − 2.94 −2.87 −2.74 3.36 3.15 2.96 2.65
MMA −18.16 0.043 − 30.9 −31.4 −31.8 − 32.7 2.68 105 2 105 1.6 105 1.1 105

absorbances measured at 270 nm. The absorbance increased linearly adsorbate is weakly bound, likely by Van der Waals forces, to the
with the concentration and became constant when the solubility is surface of MMA. The high values of K (MMA) are in line with the high
attained (Fig. 1), i.e. at the intersection of the two linear parts of the rate of adsorption.
curve. To elucidate the adsorption process, pseudo-first-order and
Several adsorption experiments showed that an equilibration time pseudo-second-order kinetic models were tested (Lagergren, 1898).
of 7 h for MMA and 4 h for MM was sufficient to achieve steady state. Better agreement was achieved for the pseudo-second-order model
The kinetics of chlorobenzene adsorption at different initial (Ho and McKay, 2000):
concentrations are presented in (Fig. 2). At low initial concentrations,    
the adsorption equilibrium is quickly reached and saturation was t 1 1
¼ þ t ð2Þ
achieved, while with high initial concentrations the adsorption was qt K2 q2e qe
slow and saturation was not reached, reaction is not complete.
The adsorption increases with increasing pH until pH 4, then where K2 is the constant rate of pseudo-second-order adsorption
decreases (Fig. 3). Thus, moderate acidity (pH = 4) is favourable. (g/(mg·min)); qt and qe are the adsorbed amount of chlorobenzene at
The heating of clay sample at higher temperatures (500 °C) leads to time t and at equilibrium (mg/g). Parameters K2 and qe were obtained
the loss of absorbed and crystalline water; this creates more open clay from the intercept and slope of the plot of (t/qt) against t (Table 3). The
structure favourable to the insertion of chlorobenzene molecules. correlation coefficient (R2) for the pseudo second order was high and
The infrared spectrum (a) of the thermal activated sample MMA the adsorbed amounts were in a good agreement with the calculated
(Fig. 4), show a reduction in the bands intensity of OH groups at (3600 values.
and 1600 cm− 1), this indicates that hydrogen bounding of interlayer To further support assertion that physical adsorption is the pre-
spaces are destructed creating then more spaces which is advanta- dominant mechanism, the activation energy (Ea) and sticking probability
geous for chlorobenzene molecules insertion. The spectrum shows (S⁎) were derived from the experimental data using a modified Arrhenius
also that MMA stability is preserved, as silanols bands Si–OH and type equation:
aluminols bands Al–OH are not modified.
 
S4 ¼ ð1−θÞexp−
Ea
ð3Þ
3.1. Isotherm modelling RT

Adsorption isotherm of chlorobenzene was expressed mathema- The sticking probability S⁎ indicates the potential of an adsorbate to
tically in terms of Langmuir and Freundlich models. Constants (K, Qm, remain on the adsorbent indefinitely, it must lie in 0 b S ⁎b 1. The plot of
KF, 1/n) are presented in (Table 1). Linearization of the Freundlich's ln (1 − θ) against 1/T was linear (Fig. 5).
relation led to the following equation: The apparent activation energy (Ea) and the sticking probability S⁎
were derived from this plot with good fit (R2 = 0.99): E = −15.8 KJ gmol− 1
1
logQ ¼ logKF þ logCeq ð1Þ indicated that lower solution temperatures favour chlorobenzene
n
adsorption and the adsorption process is exothermic. The relatively
The Eq. (1) gives a line of slope 1/n and the intercept log KF. The low value of Ea indicated that chlorobenzene adsorption is diffusion
extrapolation of this equation for C = C0, provides that C0 = constant controlled. S⁎ = 1.01 indicated that the probability of chlorobenzene
(initial concentration) which gives capacity of adsorption Qm. The sticking to MMA is very high.
Freundlich's exponent obtained between 0.58 and 0.84 indicates
favourable adsorption for chlorobenzene (0 b1/n b 1). KF is appreciable
especially for (MMA), it corresponds to more active sites while the
decrease in the 1/n can be explained as an increase in surface
heterogeneity after the thermal activation. Qm values follow the order
(MMA N MM). Good agreement is obtained between experimental
data and Freundlich data (Table 1). The results indicate that Freundlich
isotherm fit better with the experimental data than Langmuir
isotherm.
The thermodynamic values delta H and delta S were obtained by
Clausus Clapeyron equation.
ΔH°, ΔS° and energy ΔG° (Table 2) show that adsorption reaction is
spontaneous and of physical type. ΔS° near 0 indicated that the

Table 3
Constants (K1, K2) for chlorobenzene adsorption

Sample qexp (mg/g) q1 (mg/g) K1 (min− 1) R12 q2 (mg/g) K2 (g/mg min) R22
MM 5.8 12 1.5 10− 3 0.94 6.38 2.18 10− 3 0
MMA 44.42 46.53 2.3 10− 2 0.98 44.66 3.87 10− 3 0.99
Fig. 5. Activation energy of adsorption of chlorobenzene on MMA.
506 R. Sennour et al. / Applied Clay Science 43 (2009) 503–506
4. Conclusions
The adsorption potential of activated montmorillonite was
determined by adsorption of chlorobenzene from aqueous solution.
Montmorilonite modified by thermal activation showed a higher
adsorption potential than chemically activated montmorillonite (acid
and hydrogen peroxide treatment). Equilibrium was achieved within
7 h. The adsorption was pH dependant. The kinetics of the adsorption
process was of pseudo second-order type. The equilibrium data were
described by the Freundlich isotherm. The activation energy indicated
excellent sticking of the chlorobenzene molecules onto MMA. The
adsorption process was spontaneous and exothermic and the
mechanism of physical type.
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