Article

pubs.acs.org/jced

New Calix[4]arene Appended Amberlite XAD‑4 Resin with Versatile

Perchlorate Removal Efficiency
Shahabuddin Memon,* Asif Ali Bhatti, and Najma Memon
National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080, Pakistan

ABSTRACT: Perchlorate removal from an aqueous environment

was carried out by newly synthesized 25,27-bis-(N,N-dimethyl-2-
aminoethyl)carbonylmethoxy-26,28-dihydroxycalix[4]arene ap-
pended Amberlite XAD-4 resin (Resin-5). Different parameters
such as pH, dosage, concentration, interference, equilibrium
isotherms, kinetics, and thermodynamics were explored. Exper-
imental data were treated using equilibrium models such as
Freundlich, Langmuir, and the Dubinin−Radushkevich (D−R)
model, with determination of each characteristic parameter of
isotherm. The adsorption mechanism was investigated by Reich-
enberg (R−B) and Morris-Webster equations, and it is concluded
that the adsorption process is endothermic and spontaneous in
nature at higher temperature. The kinetic adsorption experiments
show that the adsorption process follows pseudo-second-order kinetics. The results show that newly synthesized resin has
capability to efficiently remove perchlorate from aqueous media.

■ INTRODUCTION
Perchlorate salts, due to their much lower costs, have been
frequently used in solid propellants of rockets/missiles, air bags,
explosives, and batteries.1−4 However, nowadays perchlorate is
attracting increasing attention as an extremely persistent
inorganic contaminant in drinking, ground, and surface
water.5−7 Lasting acquaintance to perceptible perchlorate can
cause substantial health hazards such as declined production of
thyroid hormones to humans that results in retardation of
physical and mental growths. It is also recognized as an
endocrine-disruptor chemical that leads to cancer.8−10 An
official reference dose of 0.0000291 mg·kg−1h−1 for perchlorate
has been set by Environment Protection Agency (EPA)
corresponding to a drinking water equivalent level of 24.5 μg·
L−1 in 2005.11 Thus, perchlorate removal has always been a big
task for the traditional drinking water treatment process
because of the high solubility, kinetically inert nature, and
perchlorate pollution treatment. In this regard, the supra-
molecular chemistry has provided a much improved solution in
the form of macrocyclic host compounds such as calixar-
enes.22−25 The calixarenes have been proven as an excellent
class of building blocks for the synthesis of ionophores with
almost unlimited derivatization possibilities.26 To improve the
ionophoric ability of calixarenes toward the target species,
various groups are incorporated at their lower/upper rim and
then appended within a polymeric backbone to increase their
extraction efficiency, thermal stability, and reusability.27
The aim of the current study was focused on the synthesis
and evaluation of perchlorate adsorption efficiency of new
material, that is, 25,27-bis-(N,N-dimethyl-2-aminoethyl)-
carbonylmethoxy-26,28-dihydroxycalix[4]arene appended Am-
berlite XAD-4 resin (Resin-5). Besides this, the impact of
amount and the effect of solution pH and interfering ions on
the adsorption capacity of the resin-5 has also been studied.

difficult removal of the material. Several developed technologies
have been used for perchlorate removal comprising solid phase
extraction, biological treatment, ion exchange chemical/
catalytic reduction, and membrane filtration.12−16 Of these
technologies, solid phase extraction by reason of its inexpensive,
high treatment efficiency, easy design, and operation has
attained considerable attention.
Many kinds of synthetic and natural adsorbent materials have
been used recently for perchlorate removal from aqueous
media, for example granular activated carbon amended with
cationic surfactants,17 magnetic permanently confined micelle
arrays (Mag-PCMAs),18 wheat straw,19 cross-linked quaternary
chitosan,20 and raw and oxidized carbon nanotubes,21 but the
adsorption capability of these was not so operative. Therefore,
there is a dire call for new materials and methods for
■
EXPERIMENTAL SECTION
Analytical grade reagents procured from Merck (Darmstadt,
Germany) were used for the preparation of all kinds of the
solutions. A stock standard solution 1 mol·kg−1 was prepared
using KClO4. Calibration standards were prepared by diluting
stock solution. The pH of the solution was adjusted by mixing
an appropriate amount of 0.1 mol·kg−1 (HCl/KOH). A pH
meter (781-pH/Ion Meter, Metrohm, Herisau Switzerland)
with glass electrode and internal reference electrode was used
Received: June 11, 2013
Accepted: September 8, 2013
Published: September 19, 2013

© 2013 American Chemical Society 2819 dx.doi.org/10.1021/je400554q | J. Chem. Eng. Data 2013, 58, 2819−2827
Journal of Chemical & Engineering Data
Scheme 1. Schematic Route for Synthesis of Calix[4]arene Derivative (d)
Scheme 2. Schematic Rout for Synthesis of Calix[4]arene Based Modified Amberlite XAD-4 Resin (Resin-5)
for pH measurements. Janke & Kunikel automatic shaker
model KS 501 D, Singapore, was used at ambient temperature
(25 ± 2) °C. Perchlorate analysis was done on 93 Series
Perchlorate Sensing Module ThermoOrian. Amberlite XAD-4
(surface area of 825 m2·g, pore diameter 14.4 nm, and bead size
20.50 mesh) was obtained from Fluka, Germany. All glassware
were carefully washed and soaked overnight in 3 mol·kg−1 of
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HNO3, and washed with deionized water before use. All
aqueous solutions were prepared with deionized water.
Synthesis. The compounds a, b, c and d were synthesized
by previously reported methods.28−30 New resin-5 was
synthesized according to a developed method.31 The FT-IR
spectroscopy was used to confirm the immobilization of the
resin.
dx.doi.org/10.1021/je400554q | J. Chem. Eng. Data 2013, 58, 2819−2827
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Figure 1. TGA curve of resin-5.

Characterization. The synthesized resin-5 was character-

ized through TGA/DTA and FT-IR spectroscopy. Calix[4]-
■ RESULTS AND DISCUSSION
Effect of Adsorbent Dosage and Concentration.
arene derivative (d) was appended on Amberlite XAD-4 Adsorbent dosage is a significant factor because this establishes
through diazotization and confirmed by FTIR spectra that
shows additional bands at 1704 cm−1, 1504 cm−1, and 1443
cm−1, which can be attributed to the CO, C−O, and NN
stretching, respectively.
The stability of a resin can be justified by its temperature
dependence, and it was examined by the TGA analyses. Two
key steps on thermal degradation curves are observed as shown
in Figure 1. The first step ranging from 30 °C to 150 °C is
allotted to the loss of physically adsorbed water. Another step
ranging from 250 °C to 450 °C is recognized due to the
combustion of resin-5 that shows wide room for temperature
working conditions.
Adsorption Procedure. Perchlorate adsorption was carried
out using a batch equilibration technique at ambient temper-
ature. A 10 mL sample solution containing perchlorate (1·10−4
mol·kg−1) was taken in a 25 mL Erlenmeyer flask, and resin-5
(0.1 g) was added. The mixture was equilibrated for 60 min.
After filtration, the concentration of perchlorate was examined
by a perchlorate selective electrode using a perchlorate analysis
method. As a minimum 10 concentration points including the
blank and calibration, were run in duplicate. The percent
adsorption of perchlorate was calculated as follows:
C i − Cf
% Adsorption = 100
Ci (1)
Figure 2. (a) Effect of adsorbent dosage (10 mL of perchlorate with
where Ci (mol·kg−1) and Cf (mol·kg−1) are the first and last concentration 1·10−4 mol·kg−1, 60 min contact time). (b) Effect of
concentrations of solution before and after the adsorption of concentration on adsorption capacity (0.1 g adsorbent, 10 mL of
the perchlorate, respectively. perchlorate with, 60 min contact time).
The adsorption capacity was calculated as follows:

(C i − Ce)V the capability of an adsorbent for a given initial concentration

qe =
m (2)
where qe mmol·g−1 is the adsorption capacity, Ci (mol·kg−1)
and Ce (mol·kg−1) are the initial and equilibrium concentration,
respectively, V is the volume (mL) of solution, and m the mass
(g) of adsorbent.
2821
of the adsorbate at the effective environments.32 The effect of
the amount of adsorbent on the extraction of perchlorate is
shown in Figure 2a. It was perceived that as the amount of
resin-5 increases, the adsorption of perchlorate (1·10−4 mol·
kg−1) increases due to more surface area available for
adsorption. Maximum adsorption (94.42%) was achieved at
dx.doi.org/10.1021/je400554q | J. Chem. Eng. Data 2013, 58, 2819−2827
Journal of Chemical & Engineering Data
Figure 3. Effect of pH on the percent adsorption (10 mL of
perchlorate with concentration of 1·10−4 mol·kg−1, 60 min contact
time). Schematic representation shows the proposed adsorption
mechanism at different pH values.
Figure 4. Langmuir isotherm (concn 1.90·10−5 mol·kg−1 to 1.0·10−4
mol·kg−1, 0.1 g adsorbent per 10 mL of adsorbate with 60 min shaking
time at 25 °C).
Figure 5. Freundlich isotherm (concn 1.90·10−5 mol·kg−1 to 1.0·10−4
mol·kg−1, 0.1 g adsorbent per 10 mL of adsorbate with 60 min shaking
time at 25 °C).
0.1 g of the resin-5 and adsorption remained almost constant
up to 0.15 g. There is no significant change in percent
adsorption after 0.1 g at that concentration. Keeping in view
above results further study was processed at 0.1 g of adsorbent.
Keeping the amount of adsorbent constant and effect of
adsorbate with different concentration has been performed
(Figure 2b). The maximum adsorption was found at 11.35
mmol·g−1.
Table 1. Langmuir, Freundlich and D−R Isotherm Parameters for Adsorption of Perchlorate on to Resin-5a
Q/mmol·g−1 b·104 /kg·mol−1 R2 A/kg mol−1
138.64 1258.74 0.994 0.654
a
Notation: Q, Langmuir isotherm monolayer adsorption saturation capacity; b, enthalpy of sorption; A, Freundlich isotherm multilayer adsorption
capacity; Xm, D−R isotherm maximum adsorption capacity; E, mean free energy; R2, regression coefficient.
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Figure 6. D−R isotherm (concn 1.90·10−5 mol·kg−1 to 1.0·10−4 mol·
kg−1, 0.1 g adsorbent per 10 mL of adsorbate with 60 min shaking time
at 25 °C).
pH Effect on Perchlorate Adsorption. The effect of pH
(2.5−7.5) on perchlorate adsorption by resin-5 is shown in
Figure 3.
The pH trend can be justified by the proposed mechanism
(Figure 3) for interaction of perchlorate with resin-5. At lower
pH (2.5−3.5) there is little or no interactions due to Cl−
inhibition that competes with negatively charged perchlorate as
shown in model-I. In model-II, the presence of protonated
nitrogen at moderate pH increases adsorption of perchlorate,
and as the pH goes up to neutral level, adsorption decreased
due to a decrease in protonated binding sites. The increased
adsorption of perchlorate at moderate pH could also be caused
by the endorsed electrostatic interfaces between the negatively
charged perchlorate and the positively charged ammonium ions
on resin-5.
Adsorption Isotherms. The adsorption isotherms can be
applied to predict the adsorbate behavior that has not been
experimentally investigated. Langmuir, D−R, and Freundlich
models were fitted to experimental data to examine the quantity
of the perchlorate adsorbed per unit amount of the adsorbent.
The initial concentration of adsorbate is in the range of 1.90·
10−5 mol·kg−1 to 1.0·10−4 mol·kg−1, with 0.1 g adsorbent per 10
mL of adsorbate with 60 min shaking time at 298 K. These
nonlinear isotherm models can be recast as linear equa-
tions.33−35
The Langmuir isotherm (eq 3) is based on the assumption of
monolayer surface coverage, equivalent adsorption sites, and
independent adsorption sites.
Ce 1 C
= + e
Cads Qb Q (3)
From the linear plot of Ce/Cads versus Ce (mol·kg−1), values
of Q (mol g−1) and b (kg mol−1) were calculated (Figure 4).
The separation factor RL = 1+ (1/bCi) is an essential
characteristic of the Langmuir isotherm and describes the
type of isotherm. The RL values found between 0.97 and 0.82
show favorability (0 < RL < 1) of the isotherm.36
The Freundlich isotherm (eq 4) is useful to identify
adsorption phenomena with the heterogeneous sorbent
1/n R2 Xm /mmol·g−1 E/kJ·mol−1 R2
0.425 0.960 0.761 12.90 0.977
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Table 2. Pseudo-first-order and Pseudo-second-order Kinetic Parameters for Adsorption of Perchlorate on Resin-5a
T K1/min−1 qe/mmol·g−1 R2 K2/g·mol−1·min−1 qe/mmol·g−1 R2
293 0.0741 0.0514 0.934 162.08 0.0494 0.990
303 0.0968 0.0626 0.978 47.529 0.0838 0.999
313 0.0994 0.0614 0.979 43.971 0.0879 0.994
a
Notation: k1 and k2 are the adsorption rate constants; qe, amount of adsorbent adsorbed at equilibrium, T is the working temperature; R2 is the
regression coefficient.

Figure 7. Reichenberg (R−B) plot at different temperatures for the Figure 10. Arrhenius plot for the adsorption of perchlorate on resin-5.
sorption of perchlorate on Resin-5.

Figure 11. Effect of temperature on adsorption of perchlorate ion on

resin-5.
Figure 8. Morris−Weber plot at different temperature for the
adsorption of perchlorate ion on resin-5.
Table 3. Thermodynamic Parameters for Adsorption of
Perchlorate on Resin-5a
ΔG/kJ·mol−1
−1 −1 −1
ΔH/kJ·mol ΔS/kJ·mol ·K 293 K 303 K 313 K
0.0206 0.0871 −5.02 −5.35 −6.78
ln Kc =2.06 ln Kc= 2.13 ln Kc= 2.61
a
Notation: ΔH, change in enthalpy; ΔS, change in entropy; and ΔG,
change in free energy.

Figure 9. Adsorption of perchlorate on to resin-5 as a function of time

at different temperatures.

media. Assumption of this isotherm suggests that the

adsorption sites are distributed exponentially pertaining to
the heat of adsorption.37 Figure 12. Effect of coexisting anions on perchlorate adsorption
1 efficiency of resin-5.
ln Cads = ln A + ln Ce
n (4)
where A and 1/n are the Freundlich constants, obtained from
the slope and intercept of the plot of ln Cads versus ln Ce, indicating that perchlorate is favorably adsorbed by resin-5 at
indicating the adsorption capacity and adsorption intensity, low concentration. A greater value of A also suggests that there
respectively (Figure 5). The value of 1/n < 1 (Table 1), is greater perchlorate uptake by the newly synthesized resin.
2823 dx.doi.org/10.1021/je400554q | J. Chem. Eng. Data 2013, 58, 2819−2827
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Table 4. Comparison of Resin-5 with Other Synthesized 1

E=
Materiala −2β (6)
qe/mmol·
pH g−1 ref The values of E determine the adsorption mechanism, whether
oxidized carbon nanotubes (CNTs) 4.0 0.068 21 it is physical adsorption (0−8) kJ·mol−1 or chemical ion
GAC-CTAC 2.5 0.36 43 exchange (8−16) kJ·mol−1. Herein, the extent of E is between 8
quaternary amine modified reed 10.5 3.25 44 kJ·mol−1 and 16 kJ·mol−1, which reveals that the adsorption
MIEX resin 7.0 0.96 4 process follows chemical ion exchange.39
Fe-GAC 3.0 0.16 45 Table 1 shows the value of R2 is greater in Langmuir than in
calcined Zn/Al layered double - 5.49 46 Freundlich and D−R, specifying that the adsorption process
hydroxides
favors the Langmuir isotherm; that is, the adsorbate/ion is
resin-5 1.5 11.35 present study
a chemically adsorbed.
Notation: qe, adsorption capacity. Adsorption Kinetics. The batch experiment plays a key
role in the design and evolution for the presentation of
The Dubinin−Radushkevich, (D−R) isotherm (eq 5, Figure adsorption kinetics, and can be determined by following these
6) is broader than the Langmuir isotherm as its deviances are main steps:40 internal diffusion (diffusion of molecules inside
not based on ideal assumptions such as equipotential of the pores), external diffusion (diffusion of molecules from the
adsorption positions, lack of steric hindrances between bulk phase toward the interface space), surface diffusion
adsorbed and entering units, or surface homogeneity on the
(diffusion of molecules in the surface phase), and adsorption/
microscopic level.38
desorption elementary processes. To evaluate the adsorption
ln Cads = ln X m − βε 2 (5) efficiency of sorbents, the experimental data are subjected to
−1 different kinetics equations such as Lagergren, pseudo-second-
where ε = RT ln(1 + 1/Ce), Cads (mol·g ) is the amount of
adsorbate adsorbed per unit mass of the adsorbent and Ce (mol order rate expression, and Morris−Weber and Reichenberg.41,42
kg−1) is the amount of perchlorate in liquid phase at Lagergren/pseudo-first-order and pseudo-second-order ki-
equilibrium. Xm and β are D−R isotherm constants and can netic eqs 7 and 8 are as follows:
be used to get information regarding mean free energy E (kJ·
ln(qe − qt) = ln qe − k1t
mol−1) of adsorption. (7)

Scheme 3. Regeneration Profile of Resin-5 with 0.3 mol·kg−1 HCl

2824 dx.doi.org/10.1021/je400554q | J. Chem. Eng. Data 2013, 58, 2819−2827

Journal of Chemical & Engineering Data
t
⎛ ⎞
t ⎟ ⎛⎜ 1 ⎞⎟
= ⎜⎜ 2⎟
+⎜ ⎟
qt ⎝ k 2qe ⎠ ⎝ qe ⎠ (8)
where qt (mol·g−1) is the amount of adsorbent adsorbed at time
t, qe (mol·g−1) is the amount of adsorbent adsorbed at
equilibrium and k1 (min−1) and k2 (g·mol−1·min−1) are the
adsorption rate constants. The qe and k1 and k2 were obtained
from the slope and intercept of linear plots between ln (qe − qt)
versus t and (t/qt) versus t. Table 2 shows the values calculated
from these plots. The regression coefficient (R2) values suggest
that experimental data better follows pseudo-second-order
kinetics than pseudo-first-order kinetics.
Reichenberg equation (eq 9) was used to test the adsorption
process, whether adsorption is film diffusion or intraparticle.
6e−Bt
Q=1−
π2 (9)
Rearranging the above equation in linear form we get
Bt = −0.4977 − ln(1 − Q )
where Q = qt/qm, Bt = π2Di/r2, qt and qm are adsorbed
concentration at time t and the maximum adsorption capacity,
and Di is the effective diffusion coefficient of the sorbate species
inside the sorbate particle. Di increases with increasing
temperature because at higher temperature particle diameter
increases, and as the size of effective binding sites increases,
more adsorbate will adsorb on the resin.
From the linear plot of Bt versus time t (Figure 7) the
intercept values achieved are above the origin, −0.078,
−0.0394, and −0.2055, respectively, which means that the
intraparticle diffusion is a rate controlling step with a small
friction of adsorption that occurs through film diffusion.
The Morris−Weber equation was also used to explore the
kinetic adsorption process.
qt = R d t (10)
where qt is the adsorbed concentration at time t, and Rd is
intraparticle diffusion rate constant. The linear plot of qt versus
√t (Figure 8) shows that intraparticle diffusion occurs and the
line does not pass through the origin, which means the
intraparticle diffusion is not the only rate limiting parameter
controlling the process. The value of Rd from the slope was
calculated as 0.0088 mmol·g−1·min−1/2 (293 K), 0.010 mmol·
g−1·min −1/2 (303 K) and 0.0125 mmol·g−1·min −1/2 (313 K)
with R2 values 0.987, 0.947, and 0.987, respectively. The value
of Rd increases with increasing temperature because more
collisions will occur at higher temperature between adsobate/
ion.
Thermodynamics of Adsorption. The adsorption of
perchlorate on to resin-5 was analyzed at different temper-
atures. It is noticed that as temperature increases the adsorption
capacity value increases (Figure 9). The obtained values from
the plot are 0.117 (293 K), 0.1513 (303 K), and 0.1784 mmol·
g−1 (313 K), respectively.
The temperature effect was analyzed by using the Arrhenius
equation at optimized conditions,
ln k1 = ln Ao +
Ea
RT (11)
where Ao (1/min) is the “frequency factor” and independent of
temperature, Ea (kJ·mol−1) is the activation energy, R (8.314 J·
2825
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mol−1·K−1) is the gas law constant, and T is the absolute
temperature. The value of Ea (55.4 kJ·mol−1) calculated from
the plot of ln k1 versus T−1 (Figure 10). The value of the
activation energy is in the range of (40−800) kJ·mol−1 which
suggests that the adsorption is chemical in nature.
The van’t Hoff equation (eq 12) was used for numerical
values of ΔH (kJ·mol−1), ΔS (kJ·mol·K−1), and ΔG (kJ·mol−1)
by plotting ln kc versus T−1 (Figure 11).
−ΔH ΔS
ln kc = +
RT R (12)
ΔG = −RT ln kc (13)
The evaluated thermodynamic parameters, change in
enthalpy ΔH (kJ·mol−1), change in entropy ΔS (kJ·mol−1·
K−1), and change in free energy ΔG (kJ·mol−1) are listed in
Table 3. The negative value of ΔG shows the possibility of the
adsorption process, and the decrease in ΔG values with an
increase in temperature specifies the spontaneity of the process
at higher temperature. The positive value of ΔH confirms the
endothermic process, and ΔS reveals that there is good affinity
of perchlorate toward resin-5.
Interference Effect. A study has evaluated the effect of
interference on the adsorption efficiency of resin-5 of selected
anions such as fluoride, chloride, bromide and oxyanions such
as, nitrite, nitrate, sulfate, and phosphate in varying
concentration ratios with respect to perchlorate (Figure 12)
by keeping other parameters constant. The experimental results
show that there is no major effect of these ions except sulfate
and nitrite for the removal of perchlorate by resin-5.
Reusability of Resin. The regeneration of resin-5 is
possible with the use of different concentrations of HCl,
since at particularly low pH, chloride contends with perchlorate
for the available adsorption sites onto the resin-5. Thus, the
complete desorption of perchlorate under extreme acidic
environments can be clarified by the fact that the resin-5
contains calix[4]arene derivatives with amino binding sites and
hence possesses the capability of forming hydrogen bonds with
anions. The proposed perchlorate adsorption/desorption
mechanism by resin-5 is shown in Scheme 3.
■
CONCLUSION
It could be concluded that calix[4]arene based Amberlite XAD-
4 resin (Resin-5) is an efficient adsorbent material for the
removal of perchlorate from aqueous media. The isotherm
models, and kinetic and thermodynamic studies further confirm
the experimental results. The maximum adsorption of
perchlorate could be achieved at pH 4.5. Hopefully, this
study will find its applicability in various disciplines such as
analytical, environmental, and industrial fields.
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +92 (22) 9213430. Fax: +92 (22) 9213431. E-mail:
shahabuddinmemon@yahoo.com.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We are highly thankful to the National Centre of Excellence in
Analytical Chemistry, University of Sindh, Jamshoro (Project
No. NCEAC/246/2010) for financial support.
dx.doi.org/10.1021/je400554q | J. Chem. Eng. Data 2013, 58, 2819−2827
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■
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