Colloids and Surfaces A: Physicochem. Eng.

Aspects 330 (2008) 35–41

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Adsorption of chromium(VI) from an aqueous solution

on a surfactant-modified zeolite
R. Leyva-Ramos ∗ , A. Jacobo-Azuara, P.E. Diaz-Flores, R.M. Guerrero-Coronado,
J. Mendoza-Barron, M.S. Berber-Mendoza
Centro de Investigacion y Estudios de Posgrado, Facultad de Ciencias Quimicas, Universidad Autonoma de San Luis Potosi, Av. Dr. Manuel Nava #6, San Luis Potosi, SLP 78210, Mexico

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

Article history: The adsorption equilibrium data of Cr(VI) from an aqueous solution on a surfactant-modified zeolite
Received 10 April 2008 (SMZ) was determined in a batch adsorber. The SMZ was prepared by adsorbing the cationic surfactant
Received in revised form 11 July 2008 hexadecyltrimethylammonium (HDTMA) bromide on the external surface of the zeolite. The surface area
Accepted 16 July 2008
and pore volume were determined by the N2 -BET method and it was found that the surface area and
Available online 25 July 2008
pore volume were reduced due to pore blocking caused by the surfactant molecules adsorbed on the
zeolite. The Cr(VI) was adsorbed considerably on SMZ but not on the natural zeolite. The effects of the
Keywords:
temperature and pH on the adsorption isotherm were investigated in this work. The Cr(VI) adsorption
Adsorption
Chromium (VI)
capacity of SMZ showed a maximum at pH 6 and diminished 18 and 2.7 times increasing pH from 6 to
Surfactant-modified zeolite 10 and decreasing pH from 6 to 4, respectively. The adsorption capacity was reduced by increasing the
temperature from 15 to 25 ◦ C since the adsorption of Cr(VI) on SMZ was due to an exothermic reaction.
Desorption studies showed that Cr(VI) was irreversibly adsorbed on SMZ corroborating that Cr(VI) was
chemisorbed on the SMZ. A comparison of the Cr(VI) adsorption capacities revealed that the capacities
decreased in the following order: commercial granular activated carbon > organobentonite > SMZ.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction trodialysis, reverse osmosis and adsorption on activated carbon

Some heavy metals are very toxic and exposure to these metals
represents a serious hazard for human beings and other biolog-
ical systems. In recent years, the levels of these toxic metals in
surface waters have been increasing due to pollution caused by
industrial wastewater discharges. Wastewaters from mining oper-
ations, electroplating plants, power-generating plants, electronic
appliance factories, and tanneries contain several toxic heavy met-
als. These discharges have important levels of cadmium, chromium,
copper, lead, and mercury [1].
The main chromium components of interest, due to their preva-
lence in the environment, are the trivalent form Cr(III) (chromium
oxide and chromium sulfate) and the hexavalent form Cr(VI)
(chromium trioxide, chromic acid and bichromate) [2]. Cr(VI) is
more toxic than Cr(III) since it is soluble in almost the whole pH
range and has greater mobility than Cr(III).
The most common methods employed to remove Cr(VI) from
aqueous effluents, are reduction of Cr(VI) to Cr(III) and chemical
precipitation as Cr(OH)3 , ion exchange on a polymeric resin, elec-
∗ Corresponding author. Fax: +52 444 811 7984.
E-mail address: rlr@uaslp.mx (R. Leyva-Ramos).
[3–6].
Natural zeolites are crystalline microporous aluminosilicates
with very well defined structures that consist of a framework
formed by tetrahedra of SiO4 and AlO4 . The isomorphous substi-
tution of Al3+ for Si4+ in the tetrahedra results in a negative charge
on the zeolite framework that can be balanced by exchangeable
cations. Hence, the natural zeolites can exchange cations but not
anions. It has been demonstrated that the cationic surfactants have
a great affinity to this negative charge. This property has been used
to modify the external surface of the zeolites by adsorbing a cationic
surfactant to improve its anion exchange capacity. The cationic sur-
factants that are most commonly used to modify natural zeolites
are usually long alkyl chains with a quaternary ammonium group
at one end of the chain such as hexadecyltrimethylammonium
(HDTMA) bromide [7].
The sorption of a cationic surfactant on the external surface
of a natural zeolite can be governed mainly by cationic exchange
and hydrophobic interactions [8]. At a low surfactant loading, the
surfactant cations are exchanged with the exchangeable cations
of the natural zeolite until a monolayer of surfactant cations
is formed at the external surface. At concentrations above the
critical micelle concentration, a bilayer of surfactant molecules
(admicelle) is attached to the external surface, where the outer

0927-7757/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
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36 R. Leyva-Ramos et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 330 (2008) 35–41
layer of surfactant molecules is bound by hydrophobic interactions
[9]. The external surface charge of the zeolite is changed from
negative into positive and now displays anion exchange capacity.
Haggerty and Bowman [9] studied the adsorption of CrO4 2− ,
SeO4 2− and SO4 2− oxyanions from an aqueous solution on a
surfactant-modified zeolite (SMZ) at a pH from 6.5 to 7.5, 5.8 to
7.5 and 6 to 7, respectively, and found that the three oxyanions
were adsorbed on the SMZ and that the CrO4 2− was adsorbed on
a higher extent. Moreover, desorption of these anions from the
SMZ was studied and it was found that the adsorption process was
irreversible.
Li and Bowman [10] prepared a SMZ with HDTMA-Br, –Cl and
–HSO4 − and investigated the effect of the surfactant counteranion
as well as the size of the micelle formed by different surfactants
on the SMZ capacity for adsorbing CrO4 2− . These authors reported
that the surfactant counteranion plays an important role since the
capacity of the SMZ for adsorbing CrO4 2− decreases in the following
order: HSO4 − > Br− > Cl− . In all of these works the effect of tempera-
ture and pH on the adsorption capacity of SMZ was not investigated.
The adsorption of the Cr(VI) from an aqueous solution on a
clinoptilolite modified with HDTMA-Br was studied in this work
as well as the effect of the pH and temperature on the adsorp-
tion capacity, and the reversibility of the adsorption process was
also investigated. Moreover, the capacity of the SMZ for adsorb-
ing Cr(VI) was compared with that of an activated carbon and an
organobentonite.
2. Materials and methods
2.1. Natural zeolite
The sample of zeolite rock used in this work was collected from
a mineral deposit located in the State of San Luis Potosi, Mexico.
The zeolite sample was sieved to the average particle diameter of
0.42 mm (−30 + 60 US mesh), washed several times with deion-
ized water and dried at 110 ◦ C for 24 h. This zeolite rock has been
characterized in previous works [11,12] and is mainly composed of
clinoptilolite.
2.2. Preparation of the surfactant-modified zeolite
The external surface of the clinoptilolite was modified by
adsorbing the cationic surfactant HDTMA-Br through a similar pro-
cedure proposed by Li and Bowman [10]. The maximum moles of
HDTMA adsorbed on the SMZ were 0.18 mmol/g (41.85 mg/g) [13].
2.3. Characterization of the natural zeolite and SMZ
The surface area, average pore diameter, and pore volume of the
natural zeolite and SMZ were determined by the N2 -BET method
using a surface area and porosimetry analyzer, Micromeritics, ASAP
2010. The surfaces of the natural zeolite and SMZ were examined
by using a scanning electron microscope (SEM), Leica-Cambridge,
model S420-I.
The identification of the crystalline species present in the nat-
ural zeolite and SMZ was achieved by X-ray diffraction (XRD)
analysis. XRD patterns were obtained with a diffractometer, Rigaku,
DMAX 200. The thermogravimetric analysis of the natural zeo-
lite and SMZ were carried out using a thermogravimetric analyzer
(TGA), PerkinElmer, Pyris Diamond.
2.4. Determination of Cr(VI) concentration in a water solution
The concentration of Cr(VI) in an aqueous solution was deter-
mined by an indirect colorimetric method. This method is based on
the reaction between Cr(VI) and diphenylcarbazide, that produces
a violet red color [14]. The absorbance was measured in a double
beam UV–visible spectrophotometer, Shimadzu, UV-2101 PC, at a
wavelength of 540 nm. The Cr(VI) concentration of a sample was
estimated using a calibration curve (concentration vs. absorbance)
prepared with five to seven standard Cr(VI) solutions with concen-
trations ranging from 0.1 to 0.5 mg/L.
2.5. Adsorption equilibrium data
The experimental adsorption equilibrium data were obtained in
a batch adsorber, which consisted of a 50 mL centrifuge vial made
from polypropylene with a cone-shaped bottom and a cap. The
Cr(VI) solution and the natural zeolite or SMZ were contacted in
this adsorber.
The experimental adsorption equilibrium data were obtained by
the following procedure. A solution with a known initial concentra-
tion of Cr(VI) was prepared in a 100 mL volumetric flash and a 20 mL
sample was taken and analyzed afterwards for corroborating the
initial concentration. A certain mass of the natural zeolite or SMZ
and 40 mL of the Cr(VI) solution were added to the batch adsorber.
The natural zeolite and SMZ doses used were 0.5 and 1 g, and the ini-
tial concentrations of Cr(VI) varied from 10 to 150 mg/L. The batch
adsorber was partially submerged in a constant temperature water
bath and the solution was stirred manually from 8 to 10 times daily.
The Cr(VI) solution and the adsorbent were left in contact until
equilibrium was reached. After a certain time, the adsorber solu-
tion was sampled and the Cr(VI) concentration was determined by
the colorimetric method previously described. The equilibrium was
attained when two consecutive samples showed no change in the
Cr(VI) concentration. Preliminary runs showed that 5 days was suf-
ficient time to reach equilibrium. In the constant pH experiments,
the solution pH was measured periodically with a pH meter, Accu-
ment Research, AR25, and kept constant by adding 0.1 and 0.01 M
HNO3 or NaOH solutions as required. The total volumes of the acid
and basic solutions added to the adsorber solution were registered
in order to calculate the final volume of the solution. The mass of
Cr(VI) adsorbed on the natural zeolite or SMZ was evaluated by
performing a mass balance of Cr(VI).
2.6. Desorption equilibrium data
The reversibility of the adsorption of Cr(VI) on SMZ was inves-
tigated by carrying out desorption experiments. The experimental
procedure consisted in performing an adsorption experiment as
previously described. Once equilibrium was reached, the SMZ
loaded with Cr(VI) was separated from the Cr(VI) solution by
decantation. Subsequently 40 mL of the desorbing solution with-
out Cr(VI) were poured inside the batch adsorber containing the
SMZ loaded with Cr(VI). The loaded SMZ and the desorbing solution
were left in contact for 5 days until new equilibrium was reached.
It was assumed that equilibrium was attained when the Cr(VI) con-
centration of two consecutive samples remained constant. The pH
of the solution in the desorption step was the same, lower or greater
than the pH of the solution in the adsorption step, and it was kept
constant during the desorption step as previously mentioned. The
mass of Cr(VI) that remained adsorbed on the SMZ was estimated
by a mass balance.
3. Results and discussion
3.1. Textural properties of natural zeolite and SMZ
Table 1 shows the values of the surface area, pore volume, and
average pore diameter of the natural zeolite and SMZ. The textu-
 R. Leyva-Ramos et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 330 (2008) 35–41 37

Table 1
Textural properties of the natural zeolite and SMZ

Zeolite Surface area Pore volume Average pore

(m2 /g) (cm3 /g) diameter (nm)

TAM2 21.8 0.05 9.3

SMZ 6.9 0.03 17.6

ral properties of the natural zeolite are within the range of values
reported for clinoptilolite in other works [15,16]. The surface areas
ranged between 11.4 and 30.9 m2 /g, pore volume between 0.021
and 0.058 cm3 /g, and average pore diameter from 7.3 to 9.5 nm.
The surface area and pore volume of the clinoptilolite decreased
when it was modified with the surfactant HDTMA. The decrease
in the surface area and pore volume is because the surfactant
obstructed some of the main channels of the zeolite, thus impeding
the diffusion of N2 throughout these channels. The average pore
diameter of the zeolite increased when the zeolite was modified Fig. 2. Photomicrograph of SMZ.
with the surfactant. A probable explanation is that the surfactant
blocked in a greater proportion the smallest pore diameters and
therefore, the average pore diameter increased.

3.2. Morphology of natural zeolite and SMZ

The surface of the natural zeolite and SMZ particles were

observed by using a SEM. This analysis revealed information about
the details of the surface and morphology of the particles. Fig. 1
presents a natural zeolite image that displays partially developed
crystalline laminar habits and conglomerates of compact crystals
different from those of the zeolite crystals that correspond to cer-
tain impurities such as feldspar and quartz. In addition, crystals
with a tabular habit which is typical of clinoptilolite are observed
as well as the presence of a large variety of crystal and particle sizes.
Fig. 2 shows an image of the SMZ and the laminar crystals observed
in Fig. 1, cannot be seen clearly. This is because the surfactant was
adsorbed on the external surface of the zeolite crystals.
Fig. 3. XRD pattern of the natural zeolite.
3.3. X-ray diffraction

Figs. 3 and 4 show the XRD patterns of the natural zeolite and
SMZ, respectively. The crystalline species present in the zeolite
material were identified comparing the characteristic peaks shown
in the XRD pattern with the database of the diffractometer. It was
found that the largest intensity peaks correspond to clinoptilolite
as the dominating species. Quartz (SiO2 ) was also identified as an
impurity. In the XRD pattern of the SMZ (Fig. 4) it was also noticed
that the intensity of the clinoptilolite characteristic peaks were
lessened due to the presence of the surfactant on the external
surface of the zeolite. In contrast, the relative intensity of the quartz
peak (2 around 27) increased when the zeolite was modified with
HDTMA. In other words the surfactant was mainly adsorbed on

Fig. 1. Photomicrograph of the natural zeolite. Fig. 4. XRD pattern of the SMZ.
38 R. Leyva-Ramos et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 330 (2008) 35–41

100, 250, 440 and 540 ◦ C. The first peak was due to the presence
of free water and it represents 4.8% of the initial mass of the SMZ.
The second peak occurred at a temperature of 250 ◦ C and was due
to the decomposition of the surfactant adsorbed on the SMZ. The
mass-loss represented 4.2% of the initial mass of SMZ. The peaks at
440 and 540 ◦ C were due to the further decomposition of the sur-
factant and represented 2.4% of the initial mass of SMZ. The total
mass-loss due to surfactant decomposition was 6.6%. This amount
represented a surfactant loading of 0.178 mmol surfactant/g of zeo-
lite which is in good agreement with the total moles of surfactant
adsorbed on the SMZ (0.18 mmol/g of zeolite). This result further
corroborated the presence of the surfactant on the zeolite surface.

3.5. Adsorption isotherm of Cr(VI) on natural zeolite and SMZ

The Langmuir isotherm model was fitted to the experimental

adsorption equilibrium data that is represented by the following
equation:
Fig. 5. Thermogravimetric analysis curves for the natural zeolite. qm KC
q= (1)
1 + KC
the clinoptilolite phase but not on the quartz phase. This is due to where C is the Cr(VI) concentration in the aqueous solution at equi-
that the cationic surfactants can be adsorbed on the unbalanced librium, K is a constant of the Langmuir isotherm, q is the uptake
negative charges (cationic sites) of the clinoptilolite phase. of Cr(VI) adsorbed on the natural zeolite or SMZ and qm is the
maximum uptake of Cr(VI) adsorbed on the natural zeolite or SMZ.
3.4. Thermogravimetric analysis This isotherm model was chosen because it was assumed that the
adsorption mechanism was that one anion of HCrO4 − was bound
The thermogravimetric analysis curves for the natural zeolite to an ammonium group of the surfactant adsorbed on the zeolite.
are shown in Fig. 5 and it can be observed that the mass-loss curve This mechanism can be schematically illustrated as follows:
decreased continuously until it leveled off at a temperature near
600 ◦ C. The derivative mass-loss curve of the zeolite presented only
one maximum peak at a temperature slightly above 100 ◦ C. This
mass-loss was due to free water (physically adsorbed water and
water between particles). The mass of water evolved at this tem-
perature represented 7.7% of the initial zeolite mass. The water The Langmuir isotherm constants were calculated using a least-
found within the zeolite structure is known as zeolitic water and squares method based on the Rosenbrock–Newton optimization
its peak appears at a temperature close to 200 ◦ C. Fig. 5 did not algorithm and using the following objective function:
show any peak at this temperature indicating that this clinoptilolite
did not contain any zeolitic water. Gottardi and Galli [17] reported

N
R= (qexp − qpred )2 = minimum (2)
the mass-loss curves and derivative mass-loss curves for clinop-
i=1
tilolites from different deposits and they were very similar to those
presented in this work. In addition, the absolute average percentage deviation was also
Fig. 6 shows the mass-loss and the derivative mass-loss curves estimated for each isotherm by means of the following equation:
for the SMZ and four peaks can be observed at temperatures of   
1   qexp − qpred 
N
%Dev =   × 100% (3)
N qexp
i=1

where N is the number of experimental data points, qexp is the

experimental uptake of Cr(VI) and qpred is the uptake of Cr(VI)
predicted with the Langmuir isotherm.
The Langmuir isotherm constants and the percentage devia-
tions are given in Table 2. Except for pH of 4 and 10, the Langmuir
isotherm fitted the adsorption equilibrium data for Cr(VI) onto the

Table 2
Constants of the Langmuir isotherm

Adsorbent pH T (◦ C) qm (mg/g) K × 101 (L/mg) %Dev

Organobentonite 6 25 5.12 0.365 8.16

4 25 2.10 0.598 27.8

5 25 3.32 0.179 3.61
6 25 5.19 0.153 9.39
SMZ
6 15 5.07 0.275 14.5
8 25 3.10 0.171 8.72
Fig. 6. Thermogravimetric analysis curves for the SMZ. 10 25 0.211 1.00 30.1
 R. Leyva-Ramos et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 330 (2008) 35–41
Fig. 7. Effect of the zeolite modification on the Cr(VI) adsorption capacity at pH 6
and T = 25 ◦ C.
SMZ reasonably well since the average percentage deviation was
less than 15%.
3.6. Effect of modification on the adsorption capacity of the
zeolite
The adsorption isotherms of Cr(VI) on the natural zeolite and
SMZ at T = 25 ◦ C and pH 6, are shown in Fig. 7. It can be clearly seen
that Cr(VI) was considerably adsorbed on SMZ but not on the natu-
ral zeolite. The Cr(VI) was slightly exchanged on the natural zeolite
because the natural zeolite mainly had cationic sites for exchanging
cations and the Cr(VI) in the water solution was present as an anion,
HCrO4 − or CrO4 2− . It is well documented that natural zeolites are
suitable ion exchangers for metal cations but not for anions [17]. At
an equilibrium Cr(VI) concentration of 100 mg/L, the mass of Cr(VI)
adsorbed on the SMZ was near 3.1 mg/g and that on the natural
zeolite was 0.14 mg/g. Thus, the capacity of the SMZ for adsorbing
Cr(VI) was 22 times greater than that of the natural zeolite.
The maximum moles of the HDTMA adsorbed on the exter-
nal surface of the zeolite were 0.18 mmol/g [13]. If the surfactant
molecules adsorbed on the SMZ were forming a bilayer of sur-
factant molecules (admicelle) then the moles of the ammonium
groups or positive charges available for anion exchange would be
0.09 mmol/g. At T = 25 ◦ C and pH 6, the maximum mass of Cr(VI)
adsorbed on SMZ was 4.10 mg/g (0.079 mmol/g) at a concentration
of Cr(VI) at equilibrium of 295 mg/L (see Fig. 7). It can be assumed
that Cr(VI) was only bound to 88% of the total anionic sites available
on the external surface of the SMZ.
3.7. Effect of pH on the adsorption capacity
The effect of pH on the adsorption of Cr(VI) on SMZ was inves-
tigated by obtaining adsorption equilibrium data at the pH values
of 4, 5, 6, 8 and 10. The adsorption equilibrium data as well as the
Langmuir isotherms are graphed in Fig. 8. No adsorption equilib-
rium experiments were carried out at pH above 10 because it was
observed that part of the surfactant was desorbing from the SMZ
surface.
According to the Cr(VI) speciation diagram [3], the predomi-
nant Cr(VI) species in an aqueous solution are HCrO4 − (bichromate)
and CrO4 2− (chromate). In the pH range from 2 to 4, the Cr(VI) is
mainly found as HCrO4 − and above pH 9 as CrO4 2− . At pH 6 the
39
Fig. 8. Effect of pH on the adsorption isotherm of Cr(VI) on SMZ at T = 25 ◦ C.
molar fractions of the Cr(VI) species are 74% as HCrO4 − and 26% as
CrO4 2− [3].
The effect of the solution pH on the adsorption of Cr(VI) is
illustrated in Fig. 8. This figure clearly shows that the adsorption
capacity was highly dependent upon the solution pH for the con-
centrations of Cr(VI) at equilibrium above 20 mg/L, whereas in the
pH range from 4 to 8, the adsorption capacity was slightly depen-
dent upon the pH when the concentration of Cr(VI) at equilibrium
was below 20 mg/L. At a concentration of Cr(VI) at equilibrium
greater than 20 mg/L, the maximum adsorption capacity occurred
at pH 6, and the adsorption capacity decreased 18 times while aug-
menting the pH from 6 to 10 and diminished 2.7 times reducing the
pH from 6 to 4.
The effect of the solution pH can be attributed to the electro-
static interactions between the SMZ surface and the Cr(VI) species
present in the water solution, and the selectivity of the SMZ for the
Cr(VI) species. The point of zero charge (PZC) of this SMZ was deter-
mined by a potentiometric titration method [18] and the value was
8.0 [13]. This means that the SMZ surface was negatively charged
at pH > 8 and the anionic Cr(VI) species, due to their charge, were
repelled by the SMZ surface; however, the SMZ surface was posi-
tively charged at pH < 8 and the anionic Cr(VI) species in solution
were attracted to the SMZ surface. Moreover, the surface became
even more positively charged when the solution pH was reduced
below PZC. This caused that more Cr(VI) anions were adsorbed
while reducing the pH from 8 to 6. Though, the adsorption capacity
of the SMZ diminished when the pH was further reduced from 6
to 4. The preceding behavior can be explained by recalling that at
pH 4 the predominant species was HCrO4 − (99%) whereas at pH 6
the Cr(VI) species were CrO4 2− (26%) and HCrO4 − (74%). This result
indicated that the SMZ was probably more selective for CrO4 2− than
for HCrO4 − .
3.8. Effect of temperature on the adsorption capacity
The effect of temperature on the adsorption of Cr(VI) on SMZ
was studied by obtaining the adsorption equilibrium data at tem-
peratures of 15, 25 and 35 ◦ C. The adsorption equilibrium data and
the isotherms are displayed in Fig. 9 and it can be noticed that at
T = 35 ◦ C the adsorption capacity of the SMZ was very similar to that
of the natural zeolite (see Fig. 7). This result revealed that the surfac-
tant was desorbing from the zeolite when the solution temperature
40 R. Leyva-Ramos et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 330 (2008) 35–41

Fig. 10. Adsorption of Cr(VI) on the SMZ at pH of 6 and desorption at pH of 4, 6 and

8. T = 25 ◦ C.
Fig. 9. Effect of temperature on the adsorption isotherm of Cr(VI) on SMZ at pH 6.

As it can be seen in this figure, the new equilibrium reached in the

was at 35 ◦ C. Besides, desorption of the surfactant was confirmed
by carrying out a TGA analysis of the SMZ after the adsorption
experiment at T = 35 ◦ C. The TGA analysis proved that 73.3% of sur-
factant was desorbed from the zeolite when the temperature was
increased from 25 and 35 ◦ C. Thus, the SMZ was not thermally sta-
ble at T = 35 ◦ C. No information was found regarding the thermal
stability of the SMZ in water solutions.
As shown in Fig. 9 the capacity of the SMZ for adsorbing Cr(VI)
was increased augmenting the temperature from 15 to 25 ◦ C. The
effect of temperature on K (Langmuir isotherm constant) may be
used to calculate the heat of adsorption, Had , by means of the
following equation [11]:
K = K0 e−Had /RT
The heat of adsorption was estimated to be Had =
−38.85 kJ/mol, indicating that the adsorption of Cr(VI) on SMZ
was an exothermic process. A value of Had = −35.52 kJ/mol was
reported for the adsorption of Cr(VI) on a bentonite modified
by adsorbing HDTMA [19]. Both Had are exothermic and the
values very close because in both adsorbents the Cr(VI) was being
adsorbed on HDTMA. The adsorption of Cr(VI) on SMZ was favored
by decreasing the temperature since the Cr(VI) adsorption was an
exothermic process. Moreover, Cr(VI) was probably chemisorbed
on SMZ because the magnitude of Had was very close to the heat
of a chemical reaction, which is more than 42 kJ/mol [20].
desorption step was not in the adsorption isotherm at the different
pH values, except for one data point at pH 6. This indicated that the
adsorption of Cr(VI) on SMZ was not reversible. This result further
corroborated that Cr(VI) was chemisorbed on SMZ.
The mass of Cr(VI) desorbed from the SMZ increased by raising
the pH of the desorption solution. Almost no mass of Cr(VI) was
desorbed when the desorption step was carried out at pH of 4. The
mass of Cr(VI) desorbed at pH 8 was greater than that at pH 6. It can
be argued that part of the HCrO4 − and CrO4 2− adsorbed on the SMZ
were displaced by the OH− ions in solution. Hence, more Cr(VI) was
desorbed by increasing the concentration of OH− ions.
3.10. Comparison of the Cr(VI) adsorption capacity of several
(4) adsorbent
The adsorption isotherms of Cr(VI) on activated carbon,
organobentonite and SMZ are depicted in Fig. 11. All these adsorp-
tion isotherms were determined at pH 6 and T = 25 ◦ C. A granular
activated carbon (GAC) commercially known as CG-700 and man-
ufactured from coconut shell by NOBRAC, was used in this work.

3.9. Reversibility of Cr(VI) adsorption on SMZ

The reversibility of the Cr(VI) adsorption was investigated by

carrying out two-step experiments. First, the Cr(VI) was adsorbed
on SMZ (adsorption step) and the Cr(VI) was then desorbed from
the SMZ (desorption step). The adsorption process was inverted
by decanting the SMZ loaded with Cr(VI) and adding a solution
with a determined pH but without Cr(VI). Under these conditions,
part of the Cr(VI) adsorbed on the SMZ would be desorbed and
diffused back to the solution until reaching new equilibrium. If
the adsorption of Cr(VI) on SMZ were reversible, the desorption
equilibrium data could be represented by the adsorption isotherm
determined in the adsorption step. Otherwise, the adsorption was
not reversible.
Fig. 10 shows the adsorption equilibrium data of Cr(VI) on SMZ Fig. 11. Comparison between the adsorption isotherms of Cr(VI) on activated carbon
at pH 6 and the desorption equilibrium data at pH of 4, 6 and 8. CG-700, organobentonite and SMZ at pH 6 and T = 25 ◦ C.
 R. Leyva-Ramos et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 330 (2008) 35–41
The Freundlich isotherm model was fitted to the adsorption equi-
librium data of Cr(VI) on this GAC and the isotherm constants are
plotted in Fig. 11. The organobentonite was prepared by modifying
the surface of a natural bentonite by adsorbing the cationic sur-
factant HDTMA. Further details of the procedure for preparing the
organobentonite are given elsewhere [21].
As seen in Fig. 11 the GAC had the highest capacity for adsorb-
ing Cr(VI) in comparison with the organobentonite and SMZ. The
Cr(VI) adsorption capacities decreased in the following order:
GAC > organobentonite > SMZ. The mass of Cr(VI) adsorbed at an
equilibrium Cr(VI) concentration of 20 mg/g, was 20.2, 2.16 and
1.21 mg/g for the GAC, organobentonite and SMZ, respectively. This
shows that at a concentration of Cr(VI) at equilibrium of 20 mg/g,
the capacities of GAC and organobentonite were 16.7 and 1.8 times
greater than that of SMZ.
4. Conclusions
The decrease in the surface area of the natural zeolite caused
by the surfactant adsorption was due to pore blocking. The mor-
phology of the surface observed by the SEM analysis and the mass
losses determined by the thermogravimetric analysis corroborated
the presence of the surfactant on the zeolite surface.
The Cr(VI) adsorption capacity of the natural zeolite increased
considerably due to the adsorption of the surfactant HDTMA on the
external surface of the zeolite. On the average the SMZ adsorbed 22
times more Cr(VI) than the natural zeolite.
The solution pH plays a very important role upon the adsorp-
tion of Cr(VI) from an aqueous solution on SMZ. It was observed that
the highest adsorption capacity occurred at pH 6, and the adsorp-
tion capacity was reduced either increasing the pH from 6 to 10 or
decreasing the pH from 6 to 4. This effect was ascribed to the elec-
trostatic interactions between the Cr(VI) anions in solution and the
charge of SMZ surface as well as the selectivity of the SMZ for the
Cr(VI) anions.
In the temperature range 15–25 ◦ C the Cr(VI) adsorption capac-
ity of SMZ was decreased while increasing the temperature from 15
to 25 ◦ C because the adsorption of Cr(VI) was an exothermic reac-
tion. The Cr(VI) was chemisorbed on the SMZ surface since it was
irreversibly adsorbed and the magnitude of the heat of adsorption
was close to the heat of a chemical reaction. It was found that the
SMZ was not thermally stable at T = 35 ◦ C because a great part of
the surfactant (73.3%) was desorbed from the SMZ surface when
the temperature was increased from 25 to 35 ◦ C.
The Cr(VI) adsorption capacity of various adsorbents decreased
in the following order: GAC manufactured from coconut
shell > organobentonite > SMZ. The GAC was much more effective
for adsorbing Cr(VI) that the SMZ.
Acknowledgements
This work was funded by Fondo Mixto Consejo Nacional de
Ciencia y Tecnologia (CONACyT) and San Luis Potosi through grant
41
no.: FMSLP-2002-4438 and Fondo de Ciencia Basica SEP-CONACyT
through grant no.: SEP-2003-C02-43400.
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