chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Research and Design

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

Removal of antimony (III) by multi-walled carbon nanotubes

from model solution and environmental samples

Mohamed Abdel Salam a, , Reda M. Mohamed a,b

a Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80200, Jeddah 21589, Saudi Arabia
b Advanced Materials Department, Central Metallurgical R&D Institute, CMRDI, P.O. Box 87 Helwan, Cairo, Egypt

a b s t r a c t

Multi-walled carbon nanotubes (MWCNTs) are used for the adsorption and removal of Sb(III) from model solutions
and real environmental samples. The effects of different factors that affect the adsorption process; the results showed
that most of the Sb(III) ions were removed from the solution within 30 min, at pH 7.0, using 200 mg MWCNTs. Further,
it was observed that the adsorption process was greatly enhanced by lowering the solution temperature, which
indicated the exothermic nature of the adsorption. The adsorption study was analyzed kinetically, using different
kinetic models, and the results showed that the adsorption of Sb(III) by MWCNTs from the model solution followed
pseudo-second-order kinetics with good correlation coefcients. In addition, it was found that the adsorption of
Sb(III) occurred in more than one step, including the liquid lm diffusion of the Sb(III) ions from the aqueous phase
through the liquid lm around the MWCNTs and further intra-particle diffusion through the nanotubes bundles and
aggregates.
2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Carbon nanotubes; Sb(III); Adsorption; Kinetics; Environmental samples

1. Introduction
One of the worlds major environmental problems is the
disposal of large volumes of wastewater containing heavy
metals. Most heavy metals are known to be toxic, and they
represent a severe threat to living organisms in general
and humans in particular. Consequently, their presence in
wastewater requires treatment and control before the waste-
water can be disposed. Among other toxic metals, antimony
(Sb) is one of the least studied. Antimony is present in
the environment as a result of natural processes and vari-
ous industries (Filella et al., 2002), such as semiconductors,
infrared detectors, diodes, bearing metal, pipe, rubber com-
pounds, ceramic enamels, reproof textiles, cable sheathing,
lead alloys, battery grids, plumbers solder, pewter, ammu-
nition, sheet, paints, lacquers, and certain types of matches
(Khalid et al., 2000). Antimony is a potentially toxic element
with an unknown biological function. The toxicological effects
of antimony mainly depend on its oxidation state; the Sb(III)
form, for example, is ten times more toxic than the Sb(V)
Corresponding author. Tel.: +966 541886660; fax: +966 2 6952292.
E-mail address: masalam16@hotmail.com (M.A. Salam).
Received 28 September 2012; Received in revised form 20 January 2013; Accepted 11 February 2013
0263-8762/$ see front matter 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2013.02.007
form (Gurnani et al., 1994; Gebel, 1997; Oorts et al., 2008;
Smichowski et al., 1998a, 1998b). Due to antimonys toxicity,
the European Union (EU) and the US Environmental Protec-
tion Agency (USEPA) consider antimony and its compounds
as pollutants that should be removed and regulated (Filella
et al., 2002). Traditionally, antimony-containing wastewater
is treated with different methods, such as reverse osmosis
(Kang et al., 2000), solvent extraction (Mok and Wai, 1990),
membrane ltration (Saito et al., 2004), reduction and pre-
cipitation (Gannon and Wilson, 1986), biosorption (Tomko
et al., 2006; Perez-Corona et al., 1997), sorption in a xed-
bed column (Bakir et al., 2009), ion exchange (Guin et al.,
1998), and other processes. Generally, adsorption technology
has proved to be one of the most effective techniques for
the separation and removal of heavy metals from polluted
water (Bhattacharyya and Sen Gupta, 2008; Chang et al., 2007;
Demirbas et al., 2009; Sheng et al., 2009; Srivastava et al.,
2007). Adsorption has many advantages over other treatment
methods, such as simplicity, fastness, and a lack of harmful
byproducts; moreover, both the adsorbent and the pollutants
can be regenerated. Discussions of applying the adsorption
technique for the removal of antimony from water are scarce
 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360
in the literature (Deorkar and Tavlarides, 1997; Kathrinleuz
et al., 2006; Hasany and Chaudhary, 1996; Imai et al., 1980;
Xi et al., 2011; Wu et al., 2012; Leng et al., 2012; Wang et al.,
2012; Xu et al., 2011). One of the challenges faced by adsorp-
tion technologies is the discovery of a new class of adsorbents
that could remove toxic heavy metals, such as antimony, from
aqueous solutions. Carbon nanotubes (CNTs) are a relatively
new adsorbent that have been shown to possess great poten-
tial for removing many types of pollutants. CNTs have been
successfully and efciently used for the removal of several
types of pollutants, including organic compounds (Li, 2012;
Abdel Salam et al., 2010; Abdel Salam and Burk, 2008a, 2009;
Abdel Salam and Burk, 2008b) and inorganic pollutants (Liang
et al., 2005, 2004; Staej and Pyrzynska, 2007; Rao et al., 2007;
Tuzen et al., 2008; Kosa, 2012), from various aqueous envi-
ronments. The remediation ability of CNTs, relative to other
adsorbents, is due to its strong interactions with the pollut-
ants. These interactions result from the delocalized electrons
in the hexagonal arrays of carbon atoms on the surfaces of the
CNTs.
Although there are many research studies focused on
the adsorption and removal of Sb(III) from aqueous solu-
tions by different adsorbents (Deorkar and Tavlarides, 1997;
Kathrinleuz et al., 2006; Hasany and Chaudhary, 1996; Imai
et al., 1980; Xi et al., 2011; Wu et al., 2012; Leng et al., 2012;
Wang et al., 2012; Xu et al., 2011), up to the best of authors
knowledge, there is no such study applied carbon nanotubes
as a promising and potential adsorbent. This manuscript rep-
resents the rst attempt to study the adsorption of Sb(III) from
a model solution and from real environmental samples by
MWCNTs. The effects of various operating conditions such as
adsorption time, the mass of the carbon nanotubes, solution
pH, and temperature have been studied and optimized. In
addition, the adsorption of Sb(III) from an aqueous solution by
MWCNTs at different temperatures have been studied kinet-
ically to understand the factors and transport mechanisms
that affect Sb(III) interactions with MWCNTs.
2. Materials and methods
2.1. Materials
MWCNTs with average diameters of 2040 nm were obtained
from Shenzhen Nano-Technologies, China, and were used
as received. Analytical-grade antimony nitrate (Sb[NO3 ]3 ;
Fluka, ion solution, 1000 mg L1 ) was employed to prepare
a stock solution containing 100 mg L1 of Sb(III). The stock
solution was further diluted to the desired ion concentra-
tions. All chemicals used in this study were obtained from
SigmaAldrich (analytical grade), and all solutions were pre-
pared using deionized water.
2.2. Characterization techniques
A transmission electron microscope (TEM; type JEOL JEM-1230,
operating at 120 kV, attached to a CCD camera) was used to
characterize the MWCNTs morphological structure. The spe-
cic surface areas of the MWCNTs were determined from
nitrogen adsorption/desorption isotherm measurements at
77 K, using a model NOVA 3200e automated gas sorption
system (Quantachrome, USA). The acid-base neutralization
method (Boehm titration) was performed on the prsis-
tine MWCNTs and the method was mentioned elsewhere
(Abdel Salam and Burk, 2008a). The method involved the
1353
dispersing of a certain amount of the CNTs in different aque-
ous solutions of NaOH, NaHCO3 or Na2 CO3 , left for a period
of time, centrifuge, lter and certain amount of HCl solution
was added to the supernatant to neutralize the unreacted
base, and the solutions were back-titrated with NaOH using
a potentiometer to determine the endpoint. Infrared spec-
tra measurement of the pristine MWCNTs was performed on
PerkinElmer-Universal ATR sampling accuracy Spectrum 100
FT-IR Spectrometer. Zeta potential of the MWCNTs was mea-
sured by a Malvern zetameter (Zetasizer 2000). The pH values
of MWCNTs solution were adjusted from 2.0 to 10.0 by adding
0.1 M hydrochloric acid or sodium hydroxide solution to the
glass beaker at 25 C.
2.3. Adsorption experiment
Adsorption experiments were performed to determine the
effect of time and temperature on the adsorption process and
to identify the adsorption rate. The experimental procedures
were performed as follows: (1) a series of solutions of vari-
ous Sb(III) concentrations were prepared; (2) the initial pH was
measured, and a dened amount of the MWCNTs was then
added to the solutions; (3) these solutions were agitated on
a magnetic stirrer for a certain period of time, at room tem-
perature; (4) at dened points in time, a certain volume of
the solution was removed and immediately ltered to collect
the supernatant; and (5) the residual Sb(III) concentration in
the supernatant was determined using inductively coupled
plasma-optical emission spectrometry (ICP-OES Optima 4100
DV), Perkin Elmer, USA. The amount of Sb(III) adsorbed was
determined by measuring the difference in the concentra-
tions of the samples that were obtained at two consecutive
time intervals over the course of the adsorption experiment.
The adsorption capacity of the MWCNTs qt (mol g1 ), which
represents the amount of Sb(III) adsorbed per amount of
MWCNTs was calculated using a massbalance relation-
ship:
(C0 Ct )V
q= , (1)
m
where C0 and Ct are the concentrations of Sb(III) in solution
(mol L1 ) at time t = 0 and t, respectively. V is the volume
of the solution (L), and m is the mass of the dry adsorbent
used (g). The kinetic curves obtained were analyzed using
various-order kinetic equations to obtain the parameters for
understanding the adsorption process.
2.4. Real water samples collection
Red Sea water (RSW) and wastewater samples were used
to evaluate the efciency of the MWCNTs for the removal
of the Sb(III). The Red Sea water was collected from the
Red Sea in front of Jeddah City, Saudi Arabia (latitude deg.
north 21.49555, longitude deg. east 39.16655). The wastewa-
ter sample (MBR 6000 STP) was collected from the Membrane
Bio-Reactor Technology Waste Water Treatment Plant at King
Abdulaziz University (KAUWW), Jeddah City (latitude deg.
north 21.487954, longitude deg. east 39.236748). A tap-water
(TW) sample was collected from our lab after allowing the tap
water to ow for 10 min. The RSW, KAUWW, and TW samples
were ltered through 0.45-m Millipore lter paper and kept
in Teon bottles, at 5 C, in the dark.
1354 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360
3. Results and discussion
3.1. Characterization of MWCNTs
Fig. 1 shows the transmission electron microscope images of
the used MWCNTs. The MWNTs had 1050 nm outer diam-
eters and 59 nm inner diameters. MWCNTs of various sizes
and directions were curved, forming an aggregated structure,
due to inter-molecular force. In addition, the TEM analysis ver-
ied the hollow structure of the MWCNTs. The BET-specic
surface area of the MWCNTs was calculated from the nitro-
gen adsorption/desorption isotherms at 77 K, and it was found
to be 89.2 m2 g1 . The concentrations of different acidic func-
tional groups (carboxylic, lactones and phenols) on the surface
of the pristine MWCNTs were determined qualitatively and
quantitatively using an acid-base neutralization method.
According to this method, the total concentration of the acidic
functional groups was found 0.03 0.02 mmol g1 , which is
very low and insignicant. This conrms that the surface
of the pristine CNTs was partially covered with insignicant
amount of acidic functional groups. The FT-IR measurement
to the pristine MWCNTs and the spectrum showed typi-
cal absorption peaks at 1645 cm1 and at 1450 cm1 due to
aromatic C C stretching, which are typical peaks for the
pristine MWCNTs. There were no other peaks related to sur-
face groups, except a broad peak at approximately 3500 cm1
Fig. 1 Transmittance electron microscope images at low
and high magnication power for the MWCNTS used for
Sb(III) adsorption from solution.
characteristic of an O H stretch, which might be due to the
humidity. Zeta potential measurements showed that the point
of zero charge (PZCs); at which surface charge equals to zero,
for the pristine MWCNTs was found to be 5.4, which indicated
that at a lower pH values than 5.3, the pristine MWCNYs sur-
face is positively charged and at a higher pH values, the surface
is negatively charged.
3.2. Adsorption study
3.2.1. The effect of adsorption parameters
In general, the process of adsorbing and removing any pol-
lutants from an aqueous solution by a solid adsorbent is a
function of various environmental parameters, such as adsor-
bent mass, solution pH, temperature, and the contact time
between the pollutant and the adsorbent. The effects of these
parameters on the removal of Sb(III) by MWCNTs from an
aqueous solution were investigated to optimize the adsorp-
tion process and to make the removal process more efcient.
Fig. 2 shows the effect of contact time on the adsorption of
Sb(III) from an aqueous solution by MWCNTs, using 200 mg
MWCNTs at solution pH 7.0, solution temperature 298 K, and
Sb(III) concentration 4 mg L1 . As the gure shows, the per-
centage of Sb(III) removed from the aqueous solution was
58% after 1 min, and it increased gradually to reach 80% after
30 min of adsorption and then remained constant for the rest
of the experimental time (120 min). The same observation was
reported for the biosorption of antimony by lichen biomass
(Uluozlu et al., 2010) and bentonite (Xi et al., 2011); the pro-
cesses were fast, and they reached equilibrium within 30 min
of contact time. For sodium montmorillonite, on the other
hand, the equilibrium was only achieved after 100 min (Zhao
et al., 2010). A contact time of 120 min was used for the further
studies.
The adsorbent dose is one of the crucial parameters in the
adsorption processes, as it determines the adsorbent capacity
for a given initial concentration of metal ions in a solution.
Fig. 3 shows the effect of the MWCNT dosage on the adsorp-
tion of Sb(III) from an aqueous solution at solution pH 7.0,
120 min, solution temperature 298 K, and Sb(III) concentra-
tion 4 mg L1 . It is clear from the gure that the amount
of Sb(III) adsorbed increased gradually as the MWCNT dose
Fig. 2 Effect of time on the adsorption of Sb(III) from an
aqueous solution by MWCNTs (experimental conditions:
20 ml solution, pH 7.0, 200 mg MWCNTs, 298 K, and Sb(III)
concentration 4 mg L1 ).
 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360
Fig. 3 Effect of MWCNTs mass on the adsorption of Sb(III)
from an aqueous solution (experimental conditions: 20 ml
solution, pH 7.0, 120 min, 298 K, and Sb(III) concentration
4 mg L1 ).
increased, until it reached 100% when 400 mg of MWCNTs
were used. The amount of Sb(III) adsorbed increased along
with the MWCNT dosage mainly because the higher doses
provided more available surface areas of the MWCNTs and,
consequently, more active sites available for adsorption. For
the rest of the experiment, I used a dosage of 200 mg MWC-
NTs, which corresponded to 81%, to allow a clear observation
of the other parameters effects.
Metal ions such Sb(III) are so sensitive to pH levels that they
present in different forms and may be precipitated, depend-
ing on the pH. The solution pH also greatly affects the surface
charge of the solid adsorbent. Hence, it is very important
to study the effect of the solution pH on the adsorption of
Sb(III) by MWCNTs. Fig. 4 presents the variations of the per-
centage of Sb(III) removed when using various solution pHs,
ranging from 2.0 to 11.0. At pH 2.0, the percentage of Sb(III)
removed was very low, 55.7%. This low adsorption at pH 2.0
may have been caused by the competition between the posi-
tively charged hydronium ion (H+ ), which presented at a much
higher concentration, with the Sb(III) ions for adsorption on
Fig. 4 Effect of the solution pH on the adsorption of Sb(III)
by MWCNTs (experimental conditions: 20 ml solution,
120 min, 200 mg MWCNTs, 298 K, and Sb(III) concentration
4 mg L1 ).
1355
the MWCNTs binding sites. Further, this low adsorption may
have been due to the electrostatic repulsion between the posi-
tively charged protonated carbon nanotubes and the positively
charged Sb(III) ions. Increasing the pH from 2.0 to 5.0 created
a signicant enhancement in the adsorption process, and the
percentage of Sb(III) removed increased from 55.7% to 84.4%.
This enhancement may have occurred because there was less
competition with the hydronium ions and because more active
sites were available for the binding of Sb(III). Also, the adsorp-
tion increased from pH 2.0 to 5.0 due to the decrease in the
positive charge at the surface of the pristine MWCNTs, as was
conrmed with the zeta potential measurement (Pzc = 5.3).
The positive charges over the carbon nanotubes surface usu-
ally creates electrostatic repulsion with the positively charged
Sb(III) ions. Increasing the pH from 5.0 to 8.0 and then to 11.0
led to a slight decrease in the adsorption process; the percent-
age of Sb(III) removed decreased from 84.4% to 79.1% and then
to 69.8%, respectively. These decreases in the adsorption have
may been due to the competition between the hydroxyl ions
and the Sb(III), which existed in the negative form [SbO2 ] .
The same observations were reported for the removal of anti-
mony using different solid adsorbents (Uluozlu et al., 2010;
Khalid et al., 2000; Biswas et al., 2009; Thanabalasingam and
Pickering, 1990; Xu et al., 2001). A solution pH of 7.0 was
selected for further studies.
Among the factors that greatly affect the adsorption pro-
cess, the solution temperature best reveals the suitability of
the adsorbent. To determine the effect of solution temperature
on Sb(III) removal, four different temperatures were tested:
281 K, 298 K, 323 K, and 348 K. It was observed that increasing
the solution temperature signicantly affected the adsorp-
tion of Sb(III) by the carbon nanotubes. In general, raising
the temperature from 281 K to 298 K, 323 K, and 348 K was
associated with a signicant decrease in the percentage of
Sb(III) removed, which changed from 94.8% to 79.0%, 71.6%,
and 52.2%, respectively. These results suggest an exother-
mic nature of the adsorption process, and they demonstrate
the advantage of using MWCNTs for the removal of Sb(III) at
ambient solution temperatures, without prior heating. Sim-
ilar behavior was observed when bentonite (Xi et al., 2011)
and lichen biomass (Uluozlu et al., 2010) were used as solid
adsorbents for the removal of Sb(III) from aqueous solutions.
According to the above results, the MWCNTs had an
adsorption capacity of 0.325 mg Sb(III)/g MWCNTs at pH 7.0
and 298 K. This adsorption capacity are very close to the val-
ues obtained when bentonite was applied as a solid adsorbent
(0.555 mg/g) (Xi et al., 2011), and lower than that reported for
the removal of Sb(III) with biomass (4.55 mg/g) (Wu et al., 2012),
graphene (7.463 mg/g) (Leng et al., 2012), synthetic mangan-
ite (95.5 mg/g) (Wang et al., 2012), and FeMn binary oxide
(214.24 mg/g) (Xu et al., 2011). One of the great advantages
of the MWCNTs compared with other adsorbents that the
adsorption reached equilibrium within few minutes, whereas
the adsorption took hours to attain equilibrium when other
solid adsorbents were used for the removal of Sb(III) from
aqueous solution.
3.2.2. Kinetics study
Investigating the kinetics of the adsorption of a certain pol-
lutant by a solid adsorbent involves studying the adsorption
rate to determine the effects of various factors affecting the
process. This usually occurs through the careful monitoring
of the experimental conditions that affect the speed of the
adsorption process until it reaches equilibrium. The kinetic
1356 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360
Fig. 5 Variation of the % Sb(III) adsorbed and amount
adsorbed (qt ) with the solution temperature by MWCNTs.
(Experimental conditions: 20 ml solution, pH 7.0, 120 min,
200 mg MWCNTs, and Sb(III) concentration 4 mg L1 ).
data obtained is then used to develop appropriate mathemat-
ical models to describe the interactions between the pollutant
molecules or ions and the solid adsorbent. Once the reaction
rates and the dependent factors are unambiguously known,
these results can be utilized to develop suitable adsorbent
materials for industrial applications.
Various kinetic models are used to understand the complex
dynamics of the adsorption process. The effect of tempera-
ture on the removal of Sb(III) from an aqueous solution by
MWCNTs was studied kinetically at 276 K, 298 K, and 313 K.
Fig. 5 shows the variations of the percentage of Sb(III) adsorbed
and the amount adsorbed (qt ) by MWCNTs, with the solu-
tion temperature, with time. It is clear from the gures
that the percentage of Sb(III), and consequently the qt , was
decreased by raising the solution temperature, which indi-
cated the exothermic nature of the adsorption of Sb(III) by
MWCNTs. The adsorption experimental data were treated
kinetically to understand the dynamics of the adsorption pro-
cess, using different models. The kinetics of Sb(III) adsorption
by MWCNTs were studied using the fraction power function
(Dalal, 1974), Lagergren pseudo-rst-order (Lagergren, 1898),
pseudo-second-order (Rudzinski and Plazinski, 2009), Elovich
(Rudzinski and Panczyk, 2002), intra-particle diffusion (Weber
and Morris, 1963), and liquid lm diffusion (Boyd et al., 1947)
models.
Fig. 6 Fractional power model plots of Sb(III) on MWCNTs
at different temperatures (experimental conditions: 20 ml
solution, pH 7.0, 120 min, 200 mg MWCNTs, and Sb(III)
concentration 4 mg L1 ).
The fractional power function model is a modied form of
the Freundlich equation, and it can be written in its linearized
form:
ln qt = ln a + b ln t, (2)
where qt (mg/g) is the amount of metal ion adsorbed per unit
mass of MWCNTs at any time t, while a and b are coefcients
with b < 1. The function ab is the specic sorption rate when
t = 1 min. Fig. 6 presents the application of the fractional power
function equation to the adsorption of the Sb(III) ions by
MWCNTs at different solution temperatures. Although a linear
relationship existed between ln qt and ln t, as shown in Fig. 6,
the correlation coefcients were low, especially at 313 K, as
presented in Table 1. This may show that the fractional power
function model is unsuitable for describing the adsorption of
the Sb(III) by MWCNTs.
Lagergren pseudo-rst-order kinetics is considered one of
the most commonly used equations to describe adsorption
from an aqueous solution by a solid adsorbent, and it can be
written in this way:
ln (qe qt ) = ln qe k1 t, (3)
where k1 (min1 ) is the pseudo-rst-order adsorption rate
coefcient, and qe and qt are the values of the amount
adsorbed per unit mass at equilibrium and at any time t,
respectively. When I plotted ln(qe qt ) vs. t for the four metal
ions at the four different temperatures under investigation,
the results did not converge well, and they did not provide
straight lines as shown in Table 1, which indicate that the
pseudo-rst-order Lagergren equation was not appropriate for
the description of the Sb(III) adsorption by MWCNTs.
The pseudo-second-order equation has also been consid-
ered for describing the adsorption of the Sb(III) by MWCNTs.
The linearized form of the pseudo-second-order rate equation
is given as:
t 1 t
= + , (4)
qt k2 q2e qe
 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360 1357

Table 1 Different kinetic models parameters for the

adsorption for the Sb(III) on MWCNTs at different
temperatures.
Fractional power model

Temperature A b ab R2

276 K 0.278 0.074 0.021 0.943

298 K 0.246 0.066 0.016 0.919
313 K 0.199 0.093 0.019 0.724

Pseudo-rst-order kinetic model

Temperature qe,exp (mg/g) qe,calc (mg/g) k1 R2

276 K 0.383 0.101 0.022 0.713

298 K 0.325 0.083 0.060 0.789
313 K 0.287 0.054 0.026 0.744

Pseudo-second-order kinetic model

Temperature k2 qe,exp qe,calc h R2

(g/mg min) (mg/g) (mg/g)
Fig. 7 Pseudo-second-order kinetic model plots of Sb(III)
276 K 2.68 0.383 0.385 0.397 0.999 on MWCNTs at different temperatures (experimental
298 K 4.71 0.325 0.326 0.500 0.999 conditions: 20 ml solution, pH 7.0, 120 min, 200 mg
313 K 5.91 0.287 0.287 0.489 0.999
MWCNTs, and Sb(III) concentration 4 mg L1 ).

Elovich kinetic model

of the adsorption process of Sb(III) by MWCNTs from an aque-
Temperature (g/mg min) (mg/g min) R2 ous solution, which corroborates previous studies that used
other adsorbents (Xi et al., 2011; Uluozlu et al., 2010).
276 K 3.73 106 0.024 0.961
298 K 2.42 107 0.019 0.931
The Elovich equation is another kinetic model used to
313 K 6.76 105 0.021 0.771 describe the adsorption of adsorbates, such as Sb(III), by solids
from an aqueous medium. The linear form of the Elovich equa-
Intra-particle diffusion model tion is given by the following equation:

Temperature Kid (mg/g min1/2 ) C (mg/g) R2

276 K 0.005 0.332
298 K 0.467 0.145
313 K 0.652 0.075
Liquid lm diffusion model
Temperature Kfd (min1 )
276 K 0.022
298 K 0.060
313 K 0.026
where k2 (g/[mg min]) is the pseudo-second-order rate coef-
cient, and qe and qt are the values of the amount adsorbed
per unit mass at equilibrium and at any time t, respectively.
The plot of t/qt and t in Eq. (4) must give a linear relation-
ship; based on that relationship, qe and k2 can be estimated
from the plots slope and intercept, respectively. Applying the
pseudo-second-order rate equation to the adsorption of Sb(III)
experimental data converged very well with excellent regres-
sion coefcients (R2 > 0.99) and straight lines, as presented
in Fig. 7. These ndings veried that the pseudo-second-
order model is suitable for describing the adsorption of Sb(III)
by MWCNTs from an aqueous solution. The pseudo-second-
order rate equation parameters, qe , and k2 , are calculated from
the slope and intercept of the plot of t/qt vs. t, as shown in
Table 1. The table shows that the amounts of Sb(III) adsorbed
per unit mass of MWCNTs at equilibrium (qe,calc ), calculated
from the slope of the pseudo-second-order plot, were in good
agreement with the experimental values (qe,exp ). Generally, the
amount adsorbed at equilibrium (qe ) decreased when the solu-
tion temperature increased, indicating the exothermic nature
qt = ln () + ln t, (5)
0.948
0.992 where and are the Elovich coefcients that represent the
0.984
initial adsorption rate (g/[mg min]) and the desorption coef-
cient (mg/[g min]), respectively. The Elovich coefcients and
are calculated from the slope and intercept of the qt vs. ln
R2 t plots, and their values are tabulated in Table 1. The correla-
0.657 tion coefcients were not satised, especially at 313 K, which
0.791 indicated the unsuitability of the Elovich equation to describe
0.582 the adsorption of the metal ions under investigation.
By comparing the results from the above-mentioned
kinetic models used to t the adsorption of Sb(III) experi-
mental data (i.e., the fractional power function), the Lagergren
pseudo-rst-order, the pseudo-second-order, and the Elovich
models (and, depending on the correlation coefcient val-
ues, the pseudo-second-order rate equation model) were best
suited to describe the adsorption of Sb(III) by MWCNTs from
an aqueous solution. This nding agrees well with previous
results for the adsorption of Sb(III) from aqueous solutions
using different adsorbents (Leng et al., 2012; Uluozlu et al.,
2010; Zhao et al., 2010).
Fig. 5 also demonstrates that the adsorption of Sb(III) by the
MWCNTs occurred in more than one step. The rst step (the
initial steep slope) indicated the instantaneous adsorption of
the Sb(III) ions over approximately 30 min. This steep slope
may be attributed to the diffusion of the Sb(III) ions from the
aqueous phase to the outer surfaces of the solid MWCNTs. The
initial adsorption reached equilibrium gradually, exhibiting
a classic physisorption process. The second phase exhibited
a gradual attainment of equilibrium, which may have been
due to the intra-particle diffusion of the Sb(III) ions between
the MWCNTs aggregates and bundles. The intra-particle
1358 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360
Fig. 8 Intra-particle diffusion plots of Sb(III) on MWCNTs
at different temperatures (experimental conditions: 20 ml
solution, pH 7.0, 120 min, 200 mg MWCNTs, and Sb(III)
concentration 4 mg L1 ).
diffusion model (Weber and Morris, 1963) could be expressed
by the following equation:
qt = kid t1/2 + C, (6)
where qt is the adsorption capacity at any time (t), kid is
the intra-particle diffusion rate constant (mg/g min1/2 ), and
C (mg/g) is a constant proportion to the thickness of the
boundary layer. When the intra-particle diffusion model was
applied to the Sb(III) adsorption data at different tempera-
tures, no straight lines passed through the origin, as presented
in Fig. 8. This may indicate that the intra-particle diffusion
model is not the rate-determining step. Only the last part of
the adsorption process converged well with the intra-particle
diffusion model, providing satisfactory correlation coefcient
values (>0.95), which indicated that the last step of the Sb(III)
adsorption by MWCNTs from an aqueous solution was the
inter-particle diffusion step but was not the slowest step (i.e.,
the rate-determining step).
Liquid lm diffusion, another kinetic model, assumes that
the ow of the adsorbate molecules through a liquid lm
surrounding the solid adsorbent is the slowest step in the
adsorption process (i.e., the one that determines the kinetics
of the rate processes). The liquid lm diffusion model is (Boyd
et al., 1947) given by the following equation:
ln (1 F) = kfd t, (7)
where F is the fractional attainment of equilibrium (F = qt /qe ),
and kfd (min1 ) is the lm diffusion rate coefcient. A linear
plot of ln(1 F) versus t, with a zero intercept, suggests that
the kinetics of the adsorption process are controlled by dif-
fusion through the liquid lm around the MWCNTs. As it is
clear from Table 1, the applications of the liquid lm diffusion
model to the adsorption of Sb(III) by MWCNTs from an aque-
ous solution at different temperatures did not converge and
did not provide straight lines that passed through the origin
with very low correlation coefcients; this indicated that the
diffusion of the Sb(III) ions through the liquid lm around the
MWCNTs was not the rate-determining step.
The adsorption mechanism of Sb(III) ions on MWCNTs
could be attributed mainly to the electrostatic attraction
between the positively charged metal ions and the delocalized
electrons at the MWCNTs surfaces. Accordingly, it could be
concluded that the removal of the Sb(III) by MWCNTs from
an aqueous solution occurs in different steps, including the
migration of Sb(III) ions from the bulk solution to the exter-
nal surfaces of the MWCNTs, followed by the diffusion of
metal ions through the liquid lm to the external surfaces of
the MWCNTs, followed by the adsorption of Sb(III) ions at an
active site on the MWCNTs surfaces, and nally followed by
the intra-particle diffusion and adsorption of the metal ions
through the MWCNTs aggregates.
The pseudo second-order rate constant for the removal of
heavy metal ions under investigation could be expressed as a
function of temperature by an Arrhenius-type relationship:
Ea
ln k2 = ln A (8)
RT
where Ea is the Arrhenius activation energy of adsorption, rep-
resenting the minimum energy that reactants require for the
reaction to proceed, A is the Arrhenius factor, R is the gas
constant and is equal to 8.314 J mol1 K1 , and T is the solu-
tion temperature. A linear plot was obtained between ln k2
versus 1/T for MWCNTs adsorption of the Sb(III) ions and the
adsorption activation energy was calculated from the slope.
The adsorption activation energy obtained was 15.6 kJ mol1
for Sb(III) adsorbed by the MWCNTs from an aqueous solution,
indicating that the adsorption is physical in nature, since the
physical adsorption was characterized by activation energy in
a range between 5 and 40 kJ mol1 .
3.3. Environmental applications
It is very important to use real water samples in order to
investigate the applicability of a certain type of adsorbents
to remove specic pollutants from polluted water. Three real
water samples were collected; Red Sea water (RSW), wastewa-
ter collected from the King Abdulaziz University Wastewater
(KAUWW) Treatment Plant, and tap water (TW). The concen-
tration of Sb(III) was measured for the three samples, and
the Sb(III) concentrations were found to be lower than the
detection limit of the ICP-OES. The three samples were then
spiked with 4.0 mg L1 , and 200 mg MWCNTs were added to
the solution after adjusting the pH to 7.0 and keeping the
solution temperature at 298 K; the samples were then shaken
for 120 min. The percentages of Sb(III) removed from the real
samples were found to be 81.2% (model solution), 76.3% (TW),
20.8% (RSW), and 48.3% (KAUWW) when the samples were
spiked with 4.0 mg L1 Sb(III), as noted in Fig. 9. The low per-
centage of Sb(III) removed from the RSW sample could be
attributed to the presence of very high concentrations of Na+ ,
K+ , Mg2+ , and Ca2+ , which outcompeted with Sb(III) for the
adsorption on MWCNTs and caused a screening effect (Kosa,
2012). The reduction in the percentage of Sb(III) adsorbed from
the KAUWW sample might have been due to the presence
of various pollutants that competed with Sb(III) for the same
binding sites available on the MWCNTs surfaces and conse-
quently affected the adsorption process. The percentage of
Sb(III) removed from the TW sample was similar to the per-
centage removed from the model solution, since tap water
generally contains very low concentrations of inorganic ions
and organic pollutants.
 chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360
Fig. 9 The removal of Sb(III) from different real samples by
MWCNTs (experimental conditions: 20 ml solution, pH 7.0,
120 min, 200 mg MWCNTs, 298 K, and Sb(III) concentration
4 mg L1 ).
4. Conclusions
The removal of Sb(III) from an aqueous solution by pristine
MWCNTs was studied. The effects of varying parameters that
affect the removal/adsorption process (such as contact time,
the mass of the carbon nanotubes, solution temperature, and
pH) were investigated. The results revealed that most of the
Sb(III) ions were removed from the solution within 30 min,
at pH 7.0, using 200 mg MWCNTs, at 298 K. The adsorption
of Sb(III) by MWCNTs was found to be exothermic in nature,
as the percentage of Sb(III) removed was reduced when the
solution temperature was raised. This is one of the MWC-
NTs advantages for the removal of Sb(III); they can work
effectively at low temperatures, which can reduce the costs
of water treatment. The adsorption was analyzed kinetically,
using the fraction power function, Lagergren pseudo-rst-
order, pseudo-second-order, Elovich, intra-particle diffusion,
and liquid lm diffusion models. The results showed that the
adsorption of Sb(III) by MWCNTs from a model solution was
best described, with good correlation coefcients, by pseudo-
second-order kinetics. In addition, the results showed that the
removal of the Sb(III) by MWCNTs from an aqueous solution
occurs in multiple steps, including the migration of the Sb(III)
ions from the bulk solution to the external surfaces of the
MWCNTs, followed by the diffusion of metal ions through a
liquid lm to the external surfaces of the MWCNT, followed by
the adsorption of the Sb(III) ions at active sites on the MWC-
NTs surfaces, and concluding with the intra-particle diffusion
and adsorption of metal ions through the MWCNTs aggre-
gates. The MWCNTs were used for the removal of Sb(III) from
three different real environmental samples, and the results
demonstrated the efcient removal of Sb(III).
Acknowledgements
The authors are grateful to Mr. Jaber Idrees, and Mrs. Khlood J.
Edrees for the ICP-OES analysis, Waleed Alshabaani; CHEM 491
1359
Courses student, and Mr. Tomy Savier Chundatt; King Abdu-
laziz University Wastewater Treatment Plant for providing the
waste water sample.
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