Arabian Journal of Chemistry (2015) xxx, xxxxxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Adsorption of chlorinated organic compounds from

water with cerium oxide-activated carbon composite
Khalid R. Alhooshani

Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
Received 21 October 2014; accepted 18 April 2015

KEYWORDS
Adsorption;
Cerium oxide-activated carbon composite;
Dichloromethane;
Chloroform;
Carbon tetrachloride

Abstract Adsorptive removal of dichloromethane, chloroform, and carbon tetrachloride from

aqueous solutions at 25 C by activated carbon (AC) that was loaded with cerium oxide nanoparticles (CeO2-NP/AC) was investigated. The developed adsorbent was characterized by scanning
electron microscope (SEM), FTIR spectrophotometer, X-ray diffraction (XRD), and thermal gravimetric analysis (TGA). The effect of contact time, initial concentration, and the adsorbent dosage
were also studied. The equilibrium and kinetics of adsorption were studied in a batch-type adsorption system, and the equilibrium experimental data were analyzed using Langmuir, Freundlich, and
Temkin isotherm models. Freundlich adsorption isotherm showed the best t for the equilibrium
adsorption data. Three adsorption kinetic models, pseudo rst- and second-order, and intraparticle
diffusion models were applied to test the kinetic data. Kinetic characterization of the adsorption
process onto CeO2-NP/AC is well-described by the pseudo second-order model, and the adsorption
best-t by the intraparticle diffusion model. Our study shows that at optimum conditions, 82.72%,
99.40% and 89.42% of dichloromethane, chloroform, and tetrachloride, respectively, were removed
by CeO2-NP/AC, at concentration between 0.25 and 5.00 g/L.
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1. Introduction
Treatment of wastewaters remains a serious challenge because
of the severity of environmental challenges posed by water pollution through chemical discharge. Because of the direct and
indirect impact of such discharge pollutants, it is of great
* Tel.: +966 13 860 3065; fax: +966 13 860 4277.
E-mail address: hooshani@kfupm.edu.sa.
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

concern for countries to uphold environmental protection policies and to invest in methods that can reduce the hazardous byproducts of wastewater treatment. Consequently, wastewaters
containing toxic materials such as dyestuffs, organic pollutant,
and metal ions must be treated carefully before introduction to
the environment, and the methods for removing these toxic
materials need to be further researched and improved (Chan
et al., 2011) (see Table 1).
The usage of chlorinated hydrocarbons (CHCs) in industry
has signicant impacts on the environment, and they can be
used as either reactants or solvents for the synthesis of herbicides and plastics (Meyers, 1999), industrial automotive and
aerospace solvent degreasing, dry cleaning solvents in garment
industries, precision solvent cleaning in electronic industries

http://dx.doi.org/10.1016/j.arabjc.2015.04.013
1878-5352 2015 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Alhooshani, K.R. Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite. Arabian
Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.04.013

K.R. Alhooshani
Table 1

Chemical composition of CeO2-NP/AC adsorbent.

Elements

Weight (%)

Atomic (%)

C
O
Ce
Total

52.28
4.61
43.11
100

87.96
5.82
6.22

(Peech et al., 2006; de Rivas et al., 2012), petroleum rening

(Parker, 1997), and chlorine-bleach-containing household
products (Hecht et al., 1995). Additionally, the emission from
industrial activities or wastewater streams of CHCs leads to
their dispersion into the atmosphere (Dunn and El-Halwagi,
1994), aquatic systems, and soil which pose major threats to
human and aquatic life (de Rivas et al., 2012; Giaya et al.,
2000). In addition, the presence of these chlorinated solvents
was found to cause dizziness, irregular heartbeat, reduced cognition, and nervous system impairment (Pires et al., 2001;
Sonoyama et al., 2001; Rexwinkel et al., 1999). Due to their
high volatility in ambient conditions (Sotelo et al., 2002), toxicity, strong recalcitrance to degradation, and carcinogenic
effects, CHCs have been listed as one of the priority pollutants
by United States Environmental Protection Agency (U.S.
EPA) and European Commission (EC) Erto et al., 2010.
Furthermore, these hydrocarbons can cause ozone layer depletion and formation of photochemical smog (Yun et al., 1998;
Lee et al., 2005). Due to direct and indirect harmful effects
associated with CHCs, it is of great importance to develop efcient methods for the removal of such pollutants and toxins.
The classical remediation approach employed for the removal
of CHCs is thermal incineration that involves operation at elevated temperature (1000 C). Moreover, incineration could
lead to the production of by-products such as phosgene, dioxins, and furans that are more harmful than the original contaminants (Verhulst et al., 1995; Buekens and Huang, 1998).
Other methods for removing CHCs involve catalytic oxidation or hydrodechlorination (HDC). This method utilizes different catalysts such as Pt or Pd and usually leads to a high
conversion of most reactive chloromethanes, in the order of
trichloromethane, dichloromethane and chloromethane,
(TCM > DCM > MCM). However, major issues associated
with this approach are the catalyst deactivation and the use
of high cost noble metal (Ramos-Fernandez et al., 2008;
Lemus et al., 2012; Ma et al., 2014). To offset these limitations,
there have been major advancements in the HDC approach by
the introduction of transition metals because they are more
resistant to deactivation when used as catalysts for the decomposition of chlorinated organic compounds (Ma et al., 2014,
2013). Nevertheless, these transition metal catalysts are not
completely ideal because they lead to the formation of toxic
residues such as chromium oxychloride.
Adsorption, absorption, and condensation techniques are
non-destructive techniques frequently used for the removal
or recovery of volatile organic carbons (VOCs) from gas
streams (Xu et al., 2006; Wu et al., 2008). The adsorption process is commonly used as a nal step in the treatment of
wastewater from industrial by-products for the removal of
contaminants that are signicantly resistant to biodegradation
even at very low concentration levels (Lemus et al., 2012; Erto
et al., 2010). Generally, volatile, semi-volatile and non-volatile
chlorinated organic pollutants can be efciently removed from

drinking water, surface water, and aqueous industrial sludge

by adsorption technology on the surface of activated carbon
(AC) Anfruns et al., 2011; Ren et al., 2011; Pavoni et al.,
2006, due to its unique microporous structure with high surface area, large pore volume, and high adsorption efciency
(Serrano-Ruiz et al., 2008). Although activated carbon lends
great efciencies, the commercial source for activated carbon
can be very expensive. Consequently, different alternative
sources for the production of activated carbon-like material
such as peanut shell, bagasse, sawdust, bamboo, cherry stones,
and waste tire rubber, have been developed by researchers
(Chan et al., 2011, 2008; Hamadi and Xiao, 2001; Xu and
Liu, 2008; Olivares-Mar n et al., 2009; Valix et al., 2009).
Obtaining AC from the waste tire is of great importance since
it can lower the cost of commercial ACs, eliminate re hazard
and address pollution problems associated with the disposal
process of old tires (Molino et al., 2013).
Earlier reports have described the usage of modied ACs.
For example, Pan et al. (2013) reported the adsorption and desorption of dichloromethane over metal modied activated carbons. Tsai et al. (2008) studied adsorption characteristics using
commercial activated carbon, sludge adsorbent, and activated
carbon bers, where bers showed much more adsorption.
Furthermore, Milchert et al. (2000) and Borkar et al. (2009),
use the unmodied activated carbons for the adsorption of carbon tetrachloride and dichloromethane, respectively.
Recently, there has been an increasing interest in the use of
nano-cerium oxide, CeO2, for diverse applications, such as
electrolytes in solid oxide fuel cells, insulators, high refractive
index materials, UV blockers, polishing materials, gas sensors,
high-temperature oxidation resistance, free-radical scavenger
and ultimately catalysts, catalyst promoters or catalyst supports (Sujana et al., 2008). The use of nano-cerium oxide as
catalysts is due to its high oxygen storage capacity and oxygen
donation caused by partial reduction of Ce4+/Ce3+ on the surface (Dai et al., 2008). Cerium oxide, in addition to the aforementioned advantages, CeO2 is inexpensive, highly stable,
environmentally benign, and efcient for decomposition of
chlorinated organic compounds. Incorporation of CeO2
nanoparticles onto the surface of AC is expected to improve
the adsorption efciency of CHCs compared to unmodied
AC (Lemus et al., 2012). By modifying nanoparticles on
ACs, this study will improve current costs and methods being
used for the removal of chlorinated organic compounds.
Specically, this project focuses on the preparation of ceria
nanocomposite supported on AC obtained from waste tire
rubber.
2. Materials and methods
2.1. Reagents
All chemical reagents (dichloromethane, trichloromethane,
and carbon tetrachloride (purity P 99:8%), ceric ammonium
nitrate, nitric acid, and hydrogen peroxide) were obtained
from Sigma Aldrich. Dichloromethane, trichloromethane,
and carbon tetrachloride were used without further purication. All aqueous solutions were prepared using deionized
water. The activated carbon (AC) used in this study was produced by pyrolysis process from waste rubber tires as described
by Chan et al. (2011).

Please cite this article in press as: Alhooshani, K.R. Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite. Arabian
Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.04.013

Adsorption of chlorinated organic compounds from water

2.2. Preparation of CeO2-NP/AC

Activated carbon (AC) was prepared by heating clean and
crushed waste rubber tires at 300 C to isolate the granules from
produced oil. In order to increase the porosity of the AC, the
granules were then carbonized by raising the temperature initially to 500 C for 3 h and then gradually raised to 900 C for
2 h. In addition, it was further treated with H2O2 and HNO3
to oxidize the surface of AC, producing oxygenated surface of
the AC. Then, the resultant product (AC) was washed with
excessive water and dried overnight at 100 C. The composite
of CeO2-NP/AC was prepared by co-precipitation method. In
short, 6.0 g of AC was dispersed in 150 mL of suitable media
of pH 7 by the use of a sonicator. Afterward, an equimolar solution of ceric ammonium nitrate (50 mL) was added to the mixture. The mixture was then stirred at 50 C for 24 h, followed
by reuxing it for 12 h at 90 C. Upon cooling to room temperature, the product formed was ltered, washed with water and
dried overnight at 110 C. The nal adsorbent was calcined at
350 C for 4 h in mufe furnace.
2.3. Characterization of adsorbent
To study the surface morphology of the developed adsorbent,
eld emission scanning electron microscope (FE-SEM, LYRA
3 Dual Beam, Tescan) equipped with energy dispersive X-ray
spectrometer (EDX, Oxford Instruments) was employed. The
crystalline structure of the adsorbent was investigated through
X-ray diffractometer (Shimadzu XRD Model 6000, Japan)
using Ka radiation of Cu operated at 40 kV and 30 mA.
Change on the modied surface of AC with CeO2 was studied
with Fourier transform infrared spectroscopy (FTIR) and
Thermal gravimetric analysis (TGA). FTIR spectra of adsorbent samples were obtained using a Nicolet 6700 spectrometer
(Thermo electron, USA) equipped with a deuterated triglycine
sulfate (DTGS) detector connected to OMNIC software. The
samples were prepared via the solid KBr pellet techniques.
The background correction of the spectra was performed by
16 scans with resolution 2 cm1. Thermal gravimetric analysis
(TGA) was performed using TA instruments SDT Q600
(USA). The samples were monitored at 15 C/min under nitrogen atmosphere owing at a rate of 50 mL/min. Analysis was
made over a temperature range of 20900 C.
2.4. Batch sorption procedure
Batch adsorption experiments were performed using a 125 mL
conical, airtight Pyrex glass. Each ask contained 50 mL of a
chlorinated hydrocarbons solution with varying initial concentration (C0) from 5 to 20 mg/L. The glass bottles were sealed
and then mounted on a shaker at 150 rpm until equilibrium
was achieved. The adsorption experiment was performed at
room temperature, 25 C. Parameters such as effect of initial
concentration, adsorbent dosage, and contact time were
investigated.
Chlorinated hydrocarbons adsorbed by CeO2-NP/AC composite were calculated as follows:
V
qt Co  Ct 
m

where qt is the amount of chlorinated hydrocarbons adsorbed

(mg/g), V is the solution volume (L), Co is the initial concentrations of chlorinated hydrocarbons (mg/L) at time (t = 0), Ct is
the liquid phase concentration of chlorinated organic compounds (mg/L) at any time, and m is the weight of the synthesized adsorbent (g).
2.5. Analysis of chlorinated hydrocarbons
Chlorinated hydrocarbons were determined using headspace
gas chromatography (Agilent 7890A GC) equipped with mass
selective detector (MS) (Agilent 5975C). Direct headspace
automated injection was performed by using 2.5 ml-HS syringe
with an injection of 250 lL of the headspace vapor. The 1 mL
sample was incubated at 60 C for 15 min in a 10 mL vial. The
agitation speed was 250 rpm, syringe temperature was 50 C,
and the injection speed was 500lL/s. HP-5 GC capillary column (30 m 0.32 mm i.d. 0.25 lm lm thickness) was used
for this analysis. The GCMS inlet was operated in split mode
(50:1) at 180 C. The column temperature was programmed at
35 C for 10 min and then increased to 40 C at the rate of
5 C/min for 1 min, followed by raising it to 120 C at 15 C
/min for 2 min. Finally, the temperature of GC oven was raised
to 120 C at 20 C /min and held for 11 min. Throughout the
course of these experiments, the ow of helium was maintained
at a constant ow of 1.4 mL/min. Quantications of the samples were performed in selected ion monitoring (SIM) mode,
where suitable fragments including base peaks of the compounds were boldfaced: For instance m/z 49, 84, 86, 88 for
dichloromethane; m/z 83, 85, 47 for trichloromethane and
m/z 117, 119, 121, 82 for carbon tetrachloride.
2.6. Regeneration study
The regeneration potential of spent adsorbent was determined
by using a thermal method where chlorinated adsorbed molecules were desorbed by thermal evaporation at 100 C for 24 h,
washed with de-ionized water and dried at 105 C overnight.
Then, 0.1 g of regenerated adsorbent was dispersed in 50 mL
solution containing 10 mg/L of chlorinated organic compounds and was reused for additional three cycles, following
the same procedure as fresh adsorbent.
2.7. Data analysis
The data collected from batch study at different adsorbent
dosages, and initial concentrations (5, 10, 20 mg/L) of CHCs
were analyzed by kinetic studies (pseudo-rst order, pseudosecond order, and intra-particle diffusion). In addition, different adsorption isotherm models (Langmuir isotherm,
Freundlich isotherm, and Temkin isotherm) were conducted
to identify the adsorption capacity (qt).
3. Results and discussions
3.1. Characterization of CeO2-NP/AC
The morphology of CeO2-NP/AC composite (Fig. 1a)
revealed that the surface of the composite has a large number
of nanoparticles. This, in turn, can provide additional active

Please cite this article in press as: Alhooshani, K.R. Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite. Arabian
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K.R. Alhooshani

sites for surface adsorption on the surface of activated carbon.

Based on SEM image, the average diameter of the ceria particles was estimated to be approximately 60 nm, which was further conrmed by taking the average size of the nanoparticles
from several images. The elemental analysis by EDX spectrum
(Fig. 1b) indicated the presence of carbon, oxygen, and cerium
atoms which were expected in the composite of CeO2-NP/AC
adsorbent.
The FT-IR spectrum of CeO2-NP/AC composite is illustrated in Fig. 2. Absorption frequency at 1640 cm1 represents
the enhancement in the aromatic CC groups (carbonization). The strong- and broadband at 3400 cm1 indicated the
presence of OAH of H2O, physically adsorbed on the surface.
The spectrum has absorption bands at 2900 (aliphatic CAH
stretching) and at 1054 cm1, attributed to CAO stretching
vibration. A strong absorption at 500 cm1 was assigned to
(CeAO) vibration mode (Sujana et al., 2008), conrming the
formation of cerium oxide nanoparticles. The XRD spectrum
of the activated carbon (AC) showed three broad diffraction
peaks at 2h = 2030 and 4050, which indicated the presence
of amorphous carbon disorderly stacked up by carbon rings
(Tang et al., 2012). The XRD pattern of CeO2-NP/AC composite is illustrated in Fig. 3. At low diffraction angles, the typical broad diffraction band of ceria nanoparticles was
observed, which conrmed the presence of cerium oxide
nanoparticles and their high dispersion on the AC support,
as was supported by SEM image. The diffraction peaks exhibited cubic uorite structure in comparison with JCPDS le
(PCPDF 34-0394) in the database (Lin et al., 2003). The main
phases of CeO2 are identied as (1 1 1), (2 0 0), (2 2 0) and (3 1 1),
corresponding to 2b = 28.9, 33.6, 48, and 57, respectively.
The diffraction pattern of the carbon exhibits a weak diffraction peak at 2b = 26o that is attributable to the aromatic carbon sheets oriented in a considerably random fashion.
Thermal stability of CeO2-NP/AC composite was also
investigated (Fig. 4). Thermal analysis of the prepared composites is very important to determine their thermal stability
and optimal conditions of calcination. As shown in the gure,
the CeO2/AC has shown better thermal stability than bare synthesized activated carbon. The total weight loss of 9% was
observed in the CeO2-NP/AC composite adsorbent which
can be attributed to decomposition of adsorbed water molecules. On above 400 C, almost no weight loss was further
observed, conrming the presence of crystalline CeO2 on the
activated carbon as the nal adsorbent. In case of AC, no

Figure 1

% Transmittance

CeO2-NP/AC
AC

500

1000

1500

2000

2500

3000

3500

-1

Wavenumber (cm )

Figure 2 FTIR
composite.

spectrum

of

as-developed

CeO2-NP/AC

Figure 3 X-ray Diffractogram patterns of (a) AC (from waste

rubber tire), (b) as-developed CeO2-NP/AC composite.

signicant weight loss was observed at almost 500 C except

approximately 18% weight loss at above 100 C, due to
adsorbed water.

(a) SEM images of the surface structure of the CeO2-NP/AC, (b) EDX analysis of CeO2-NP/AC.

Please cite this article in press as: Alhooshani, K.R. Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite. Arabian
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Adsorption of chlorinated organic compounds from water

110

Weight (%)

100

Ceria NPs-AC

AC

90
80
70
60
50
40
0

100

200

300

400

500

600

700

800

900

1000

Temperature (C)

Figure 4 Thermogravimetry analysis of both bare AC and

CeO2-NP/AC composite.

3.2. Effect of contact time and initial concentration

The effect of contact time on the removal capacity of chlorinated hydrocarbons by CeO2-NP/AC composite, as illustrated
in Fig. 5, revealed that the removal of chlorinated hydrocarbons increased quickly with a contact time and then progressed at a slower rate until it reached the saturation step.
This result is due to the large number of active sites on the
external surface of the adsorbent. Consequently, the initial step
of the adsorption was initially very fast which was slowed
down due to internal diffusion process. Moreover, the large
number of vacant active sites observed after a certain time
indicated that the uptake of the solute molecules was made difcult due to the repulsive forces between the solute molecules
on the surface of the CeO2-NP/AC as well as in the bulk
phases (Wu et al., 2008; Aroua et al., 2008). However, the
quantity of chlorinated hydrocarbons adsorbed per unit mass
of CeO2-NP/AC was increased as the initial concentration of
chlorinated hydrocarbons was increased. This was attributed
to the increase in mass transfer between the solution and the

The amount of the adsorbent is considered a signicant factor

because it can identify the capacity of the adsorption for a
given initial concentration of the adsorbate (Ouazene, 2010).
Fig. 6 shows the effect of CeO2-NP/AC dosage on the removal
of chlorinated hydrocarbons. Different adsorbent dosages
were applied for dichloromethane, chloroform, and carbon
tetrachloride at initial concentration of 10 mg/L, at 25 C,
and at a shaking time of 60 min. The results indicated that,
the percent removal of chlorinated hydrocarbons was
increased from 32.04% to 82.72% for dichloromethane, from
57.14% to 99.40% for chloroform and from 71.74% to
89.42% for carbon tetrachloride, with an increase of adsorbent
dosage from 0.25 to 5.00 g/L. This increase could be attributed
to the large vacant sites of the increased adsorbent mass, for a
constant concentration of chlorinated hydrocarbons (Li et al.,
2003; Gupta, 2008). However, when the adsorbent dose
exceeded 3 g/L, the increase in percent removal of chlorinated
hydrocarbons was insignicant (Mittal, 2005; Gupta et al.,
2011). The removal percentage of chlorinated hydrocarbons
in solution was calculated by Eq. (2) as follows:
%Removal

10
8

q (mg/g)
t

3.3. Effect of adsorbent dosage

20 mg/L
10 mg/L
5 mg/L

q (mg/g)
t

adsorbent by virtue of concentration factor, a driving force

in the adsorption process (Garg, 2003; Selvi et al., 2001).
The amount of chlorinated hydrocarbons adsorbed per gram
of CeO2-NP/AC after 10 min increased from 1.47 to
8.80 mg/g for dichloromethane, 3.4015.99 mg/g for chloroform and from 4.58 to 18.61 mg/g for carbon tetrachloride
when the initial chlorinated hydrocarbons concentration was
increased from 5 to 20 mg/L. Therefore, the adsorption was
very rapid in the rst 10 min and then was decreased and
remained constant at the equilibrium, which was reached in
almost 30 min.

4
2

Co  Ce
 100
Co

15
20 mg/L
10 mg/L
5 mg/L

12
9
6
3

0
0

20

40

60

80

100

120

20

40

80

100

120

20
15

q (mg/g)
t

60

Time (min)

Time (min)

20 mg/L
10 mg/L
5 mg/L

10
5
0
0

20

40

60

80

100

120

Time (min)

Figure 5 Effect of contact time on adsorption of (a) dichloromethane, (b) chloroform, (c) carbon tetrachloride at different
concentrations, and temperature 25 C.

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K.R. Alhooshani
100
90

3.4.1. The pseudo-rst order model

Dichloromethane

Chloroform

Carbon tetrachloride

The pseudo-rst order equation was used to examine the

kinetic adsorption data collected at three different initial concentrations of chlorinated hydrocarbons for investigating the
rate-controlling mechanism of the adsorption process (Sari,
2008). The pseudo-rst order kinetic model can be described
by the following Lagergren rate equation (Lagergren, 1898):

80

Removal %

70
60
50
40
30

logqe  qt

20
10
0

0.3

0.5

1.0

2.0

5.0

CeO2NP/AC dosage (g/L)

Figure 6 Effect of adsorbent dosage on the adsorption of

dichloromethane, chloroform and carbon tetrachloride at different
concentrations, and temperature 25 C.

3.4. Adsorption kinetics

The adsorption rate gives important information for designing
batch adsorption systems. McKay et al., demonstrated that the
adsorption process is composed of three steps: (1) (lm resistance); which involves transfer of solute from the bulk solution
to the external surface of the sorbent through a liquid boundary layer; (2) (intraparticle resistance) which is the transfer of
solute from the sorbent surface to the intraparticle active sites
and (3) (reaction resistance) interactions of the solute with the
vacant sites on both the external and internal surfaces of the
sorbent (McKay, 1984). Additionally, the adsorption kinetic
information describes the interaction between adsorbent and
solution interface and can determine the mechanism of the
adsorption processes. Such a mechanism might be explained
by the pseudo rst-order, pseudo second-order rate equation
(Ho and Chiang, 2001), and intraparticle diffusion models
(Wang and Zhu, 2008). The agreement between experimental
results and the kinetic model expected values is indicated by
the correlation coefcient (R2).
1.0

Log (qe-qt)

0.0
-0.5
-1.0
-1.5

10

20

30

40

50

60

70

80

3.4.2. The pseudo-second order model

The pseudo second-order adsorption kinetic rate equation was
expressed by the following equation (Ho et al., 2000):
dqt
k2 qe  qt 2
dt

where k2 is the rate constant of the pseudo-second-order

adsorption (g/mg.min), and qe and qt are the adsorbed
amounts of the chlorinated hydrocarbons in mg/g of adsorbate
at equilibrium and time, t, respectively. When the boundary
conditions are applied from t = 0 to t = t and qt = 0 to
qt = qe, the Eq. (4) after the integration becomes

20 mg/L
10mg/L
5 mg/L

0.5

1.0

0.0
-0.5
-1.0
-1.5

90

20 mg/L
10mg/L
5 mg/L

0.5

10

20

30

1.0

50

60

70

80

90

20 mg/L
10mg/L
5 mg/L

0.5

Log (qe-qt)

40

Time (min)

Time (min)

where k1 is Lagergren rate constant of pseudo-rst-order

adsorption (1/min), and qt and qe are the amounts of chlorinated hydrocarbons (mg/g) at contact time t and at equilibrium, respectively. From the plots of log qe  qt versus t
(Fig. 7), the values of k1 (rate constant) and qe (adsorption
quantity) at equilibrium were calculated from the slopes and
intercepts. These values are given in Table 2.
The obtained correlation coefcient (R2) values from the
plots were low for the three concentrations of chlorinated compounds, which indicated the lack of linearity for pseudo-rstorder kinetic model. The correlation between the calculated
qe from the Eq. (3) and observed qe was very poor. This indicated that the adsorption of chlorinated hydrocarbons did not
obey the pseudo-rst-order kinetic model and, consequently,
the mechanism of the adsorption on the surface of the CeO2NP/AC may not follow the pseudo-rst-order model well.

Log (qe-qt)

k1
t
2:303

0.0
-0.5
-1.0
-1.5

10

20

30

40

50

60

70

80

90

Time (min)

Figure 7 Lagergren rst order plot for adsorption of (a) dichloromethane, (b) chloroform, (c) Carbon tetrachloride at different
concentrations and temperature 25 C.

Please cite this article in press as: Alhooshani, K.R. Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite. Arabian
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Adsorption of chlorinated organic compounds from water

Table 2

Kinetic constant parameters obtained from chlorinated hydrocarbons adsorption on CeO2-NP/AC.

Compound

CH2Cl2

CHCl3

CCl4

Pseudo-rst order

Pseudo-second order

Intraparticle diusion model

Ci (mg/
L)

qeexp
(mg/g)

k1 (103)
(min1)

qecal
(mg/g)

R2

k2 (103) (g/
mg min)

qecal
(mg/g)

R2

kid (mg/
g min)

C (mg/
g)

R2

20
10
5
20
10
5
20
10
5

9.57
5.67
2.97
15.64
8.52
4.73
19.53
8.42
4.18

23.491
18.194
20.004
27.406
21.418
25.794
28.327
32.012
26.945

172.139
85.949
4.802
131.033
49.424
83.538
66.119
18.926
78.415

0.8894
0.9071
0.9355
0.9503
0.9398
0.952
0.9758
0.872
0.9732

0.234
0.800
3.033
0.989
2.112
0.121
2.551
4.344
11.527

12.24
6.45
3.20
16.08
8.83
4.79
19.81
8.59
4.25

0.9906
0.9912
0.9973
0.9995
0.9992
1.0000
1.0000
0.9999
1.0000

0.6706
0.2771
0.098
0.402
0.1795
0.0358
0.1997
0.0952
0.0379

2.3938
2.6065
1.9182
11.435
6.5962
4.3556
17.475
7.4244
3.7897

0.9758
0.9662
0.9685
0.9749
0.9749
0.9828
0.9493
0.9552
0.9844

1
1
k2 t
qe  qt qe

values (R2 = 0.99) from all the data at different concentrations

indicates that the adsorption kinetics between CeO2-NP/AC
composite and the chlorinated hydrocarbons follow the
pseudo-second order (Rodrigues et al., 2010).

Eq. (5) represents the integrated rate law for pseudo-secondorder and it can be expressed in the linear form as below:
t
1
t

qt k2 q2e qe

3.4.3. The intraparticle diffusion model

The investigation for the possibility of intraparticle diffusion

and prediction of the rate controlling step in the adsorption
process was carried out by using the Weber and Morris model
(Weber, 1963; Wu, 2007). The rate constants of intra-particle
diffusion (kid) can be determined by using the following
equation:

where h is the initial adsorption rate at t = 0, and h (mg/g.min)

can be described as
h k2 q2e

Therefore, Eq. (7) can be written in a form as

t
1 t

qt h qe

qt kid t2 C

where qt is the amount of chlorinated hydrocarbons adsorbed

at time t, t1/2 is the square root of the time, C is the intercept
referring to the thickness of the boundary layer, and the larger
the intercept, the greater the boundary layer effect. If intraparticle diffusion occurs, then qt versus t1/2 will be linear and
if the plot passes through the origin, then the rate limiting process is only due to the intraparticle diffusion. Otherwise, some

The plots of t/qt against t of Eq. (6) at different initial concentrations (5, 10 and 20 mg/L) of the chlorinated hydrocarbons are shown in Fig. 8. The adsorption parameters qe, and
k2 were calculated from the slope and the intercept respectively
as shown in Table 2. The agreement between the calculated qe,
and experimental qe, and the observed correlation coefcient

25

20 mg/L
10 mg/L
5 mg/L

20

t/g (min.g/mg)

t/g (min.g/mg)

15
10
5
0

20

40

60

80

100

30
20
10
0

120

20 mg/L
10 mg/L
5 mg/L

40

10 20 30 40 50 60 70 80 90 100 110 120

Time (min)

t/g (min.g/mg)

Time (min)

30

20 mg/L
10 mg/L

25

5 mg/L

20
15
10
5
0
20

40

60

80

100

120

Time (min)

Figure 8 Linear regression of kinetics Plot: pseudo second order for (a) dichloromethane, (b) Chloroform, (c) Carbon tetrachloride at
different concentrations and temperature 25 C.

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K.R. Alhooshani

other mechanisms along with intraparticle diffusion are also

involved (Tan et al., 2009). The plots of qt versus t1/2 are illustrated in Fig. 9. The lines of the different concentration do not
go through the point of origin which means the mechanism
cannot determine the rate of the overall process, and the
adsorption mechanism is likely to be very complex (Cunha
et al., 2010).

the type of the isotherm and the nature of the adsorption

process. Regarding the RL value, adsorption can be unfavorable (RL > 0), linear (RL = 1), favorable (0 < RL < 1) or
irreversible (RL = 0) Weber, 1974. The plots of Ce/qe versus
Ce show high linearity conrmed by the values of the correlation coefcient R2, which indicated that the isotherm data
t this model; however, the R2 obtained for Freundlich
model tted more than the Langmuir model as shown in
Table 3.

3.5. Adsorption isotherm

3.5.2. Freundlich isotherm model

Various isotherm models were used for investigation of

adsorption capacity in adsorption of chlorinated hydrocarbon
from aqueous solution. The three models introduced in this
study are Langmuir, Freundlich, and Temkin isotherms.

The Freundlich model is usually used to explain the adsorption

by a heterogeneous surface of an adsorbent (Freundlich, 1906).
The well-known logarithmic form of Freundlich is dened by
the following equation:

3.5.1. Langmuir isotherm model

1
lnqe lnKf lnCe
n

The Langmuir explains that the adsorption process occurs on

the homogeneous surface of the adsorbent by monolayer of the
adsorbate which has specic active sites and energies (Hameed,
2006; Langmuir, 1916; Deng et al., 2009). The linear equation
is given by
Ce
1
Ce

qe kL qm qm

where Kf (L/g) and n are Freundlich constants related to

adsorption capacity and adsorption intensity, respectively.
The slope and intercept of straight portion of the linear plot
were obtained by plotting ln(qe) versus ln(Ce) Fig. 11. The
Freundlich isotherm constants Kf and n were calculated as represented in Table 3. It is interesting to see that all values of
1/n > 1 represent favorable adsorption condition (Treybal,
1968; Poots and Healy, 1978; Ho and McKay, 1998). The correlation coefcient is used as a tool to determine the best tting
parameters for each model, and to determine the adsorption
process that is observed. It is observed that the linearity coefcient for all the CHCs was high, and this gives better indication that the adsorption process is followed by the Freundlich
isotherm (Canzano et al., 2014). The correlation coefcient
(R2) of 0.997, 0.998, and 0.996 for dichloromethane, chloroform and carbon tetrachloride, respectively, indicated that
the adsorption process could be best described by Freundlich
isotherm.

10

where kL is Langmuir equilibrium constant (L/mg), and qm

(mg/g) is the monolayer adsorption capacity, which were calculated from a plot Ce/qe versus Ce (adsorbed equilibrium concentration) Fig. 10. The characteristic parameter of Langmuir
isotherm can be illustrated in terms of dimensionless equilibrium parameter, RL, known as separation factor, dened by
Weber and Chakkravorti as follows:
RL

1
1 KL Co

11

where Co in this case is the highest initial solute concentration. The value of separation factor gives an indication for

10
9

qt (mg/g)

qt (mg/g)

16
14

8
20 mg/L
10 mg/L
5 mg/L

7
6
5
4

20 mg/L
10 mg/L
5 mg/L

12
10
8
6

3
2

12

1/2

(min)

10

1/2

(min)

10

12

1/2

20
18
20 mg/L
10 mg/L
5 mg/L

16

qt (mg/g)

1/2

14
12
10
8
6
4
2

1/2

(min)

10

12

1/2

Figure 9 Intraparticle diffusion kinetic plot for (a) dichloromethane, (b) chloroform, (c) carbon tetrachloride at different concentrations
and temperature 25 C.

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Adsorption of chlorinated organic compounds from water

1.4

0.5

1.2

0.4

1.0

0.3

Ce/qe

Ce/qe

0.8
0.6
0.4

0.2
0.1

0.2

0.0

0.0

-0.1
0.0

Ce (mg/L)

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Ce (mg/L)

0.35
0.30

Ce/qe

0.25
0.20
0.15
0.10
0.05

1.0

1.5

2.0

2.5

Ce (mg/L)

Figure 10 Langmuir model for adsorption of (a) dichloromethane, (b) chloroform, (c) carbon tetrachloride at different concentrations,
and temperature 25 C.

Table 3

Langmuir, Freundlich, and Temkin isotherm constants for chlorinated hydrocarbon adsorption on CeO2-NP/AC.

Compound

CH2Cl2
CH3Cl
CCl4

Langmuir isotherm constants

Freundlich isotherm constants

2

T (K)

qm (mg/g)

kL (L/mg)

RL

298.16
298.16
298.16

3.476
7.283
7.289

0.750
7.151
5.532

0.118
0.014
0.018

0.986
0.983
0.985

0.5

KF

1.802
1.049
1.303

0.555
0.954
0.768

17.167
8.602
9.319

0.997
0.998
0.996

kT (L/gm)

bT (kJ/mol)

R2

0.474
3.170
0.461

2.705
33.008
11.197

0.929
0.666
0.996

0.0
-1.5

-0.5

ln qe

ln qe

1/n

0.0

Temkin isotherm constants

-1.0
-1.5

-3.0
-4.5
-6.0

-2.0
0.5

1.0

1.5

2.0

-4

-3

-2

ln Ce

-1

ln Ce
-0.9

ln qe

-1.2
-1.5
-1.8
-2.1
-2.4
-0.2

0.0

0.2

0.4

0.6

0.8

1.0

ln Ce

Figure 11 Freundlich model for adsorption of (a) dichloromethane, (b) Chloroform, (c) Carbon tetrachloride at different
concentrations, and temperature 25 C.

3.5.3. Temkin isotherm model

The Temkin isotherm represents the quantity of heat needed
for the adsorption by one layer of adsorbate on the surface
of adsorbent. The linear form of Temkin model is given by

lnqe

RT
RT
ln KT
ln Ce
bT
bT

13

where bT is the Temkin constant related to the heat of sorption

(kJ mol1), KT is the equilibrium binding constant which is

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K.R. Alhooshani

1.4

qe (mg/g)

10

1.0

0.5

0.4

qe (mg/g)

1.2
0.8
0.6
0.4

0.3
0.2
0.1
0.0
-0.1

0.2
0.0
0.0

0.5

1.0

1.5

2.0

-0.2
-5

-4

-3

ln Ce

-2

-1

ln Ce
0.30

qe (mg/g)

0.25
0.20
0.15
0.10
0.05
0.00
-0.2

0.0

0.2

0.4

0.6

0.8

1.0

ln Ce

Figure 12 Temkin model for adsorption of (a) dichloromethane, (b) Chloroform, (c) Carbon tetrachloride at different concentrations,
and temperature 25 C.

equal to the maximum binding energy (L g1), R is gas constant (8.31441 J mol1 K1) and T is the absolute temperature
(K) Idrisa and Ahmad, 2011. The plot of qe versus ln(Ce) is
illustrated in Fig. 12, and the isotherm constants were determined from the slope and intercept Table 3. The R2 in this case
was low compared to the other two models described above,
especially in the case of chloroform that shows poor accuracy
in the experimental data tting using Temkin model. This
observation suggested that the adsorption of chloroform compound on the adsorbent does not occur through a uniform distribution adsorbent-adsorbate interaction or mechanism.
3.6. Regeneration of adsorbents
The disposal of adsorbent as by-products in the adsorption
process is not economical. Therefore, regeneration of the
adsorbent is highly desirable (Yogesh Kumar et al., 2013). In
order to be cost effective, adsorbent was regenerated by thermal treatment. Thereafter, the regenerated adsorbent material
was tested for additional three cycles, and the results showed
excellent reusability with almost percentage removal of
100
Original adsorbent

Recycle-1

Recycle-2

Recycle-3

chlorinated compounds compared with fresh adsorbent, as

shown in Fig. 13.
4. Conclusions
An efcient and fast adsorptive removal of dichloromethane,
trichloromethane and carbon tetrachloride from aqueous
media at ambient conditions was achieved by using AC loaded
with cerium oxide nanoparticles (CeO2-NP/AC). The adsorption removal of tested organic chlorinated compounds onto
CeO2-NP/AC composite can be well described by Freundlich
adsorption isotherm. Kinetic characterization of the adsorption process onto the developed adsorbent was well described
by the pseudo second-order model, and the adsorption t the
intraparticle diffusion model. Among the features, fast equilibrium time, high adsorption capacity as well as efcient adsorbent regeneration indicated that the CeO2-NP/AC is a highly
efcient low cost adsorbent for the removal of dichloromethane, chloroform, and carbon tetrachloride from aqueous
media.
Acknowledgements

90

The nancial support provided by King Abdulaziz City for

Science and Technology (KACST), Riyadh, Saudi Arabia,
through summer research fund and facility support provided
by the King Fahd University of Petroleum & Minerals,
Dhahran, Saudi Arabia for this work are gratefully
acknowledged.

Removal (%)

80
70
60
50
40
30
20

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10
0

(a) CH2Cl2

(b) CHCl3

(c) CCl 4

Figure 13 Reusability of adsorbent (CeO2-NP/AC) for additional three cycles after the initial use for adsorption of (a)
dichloromethane, (b) Chloroform, (c) Carbon tetrachloride at
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Please cite this article in press as: Alhooshani, K.R. Adsorption of chlorinated organic compounds from water with cerium oxide-activated carbon composite. Arabian
Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.04.013