Ultrasonics Sonochemistry 15 (2008) 1033–1037

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Combined effect of ultrasound and nanoclay on adsorption of phenol

Shirish Sonawane a,*, Prashant Chaudhari b, Shailesh Ghodke b, Swapnil Ambade a, Suhas Gulig a,
Ameya Mirikar a, Abhishek Bane a
a
Department of Chemical Engineering, Vishwakarma Institute of Technology, 666 Upper Indira Nagar Bibwewadi, Pune, Maharashtra 411037, India
b
Nanoscience and Engineering Research Group, University Department of Chemical Technology, North Maharashtra University, Jalgaon, Maharashtra 425001, India

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

Article history: Sorption of phenol onto organophilic bentonite (nanoclay) by ultrasonic irradiation was investigated. Tet-
Received 26 October 2007 rabutyl ammonium chloride (TBAC), N-acetyl-N,N,N trimethyl ammonium bromide (CTAB) and hexadecyl
Received in revised form 11 February 2008 trimethyl ammonium chloride (HDTMA) were used as intercalating agents. Nanoclay was synthesized
Accepted 12 March 2008
using sonication technique. TBAC modified nanoclay shows amorphous exfoliated nature, while CTAB
Available online 28 March 2008
and HDTMA modified nanoclay shows intercalating crystalline nature, which was revealed by XRD gram.
Further FTIR reveals the presence of NH2 and (CH2)n groups onto clay platelet. Due to sonication, adsorp-
Keywords:
tion equilibrium was achieved within short period of time (10 min). It was found that intraparticle diffu-
Ultrasound
Phenol
sion resistance has overcome due to sonication. The experimental data obtained obeys both Freundlich
Adsorption isotherm model and Langmuir adsorption isotherm model. HDTMA modified nanoclay shows higher
Nanoclay parameter values.
Ó 2008 Elsevier B.V. All rights reserved.

1. Introduction was investigated. The conclusion was drawn based on fitting of

Phenols are widely used in the industry such as paint, resin,
pharmaceutical and agrochemicals [1]. Activated carbons are the
most widely used adsorbents because they have excellent adsorp-
tion capabilities for phenols. However, the use of granular or pow-
dered activated carbons is often suffered from relatively slow
adsorption rate due to their microporous structures and long diffu-
sion path [2]. Use of sonication for phenol removal has proved to
be an attractive process over the years at least on a laboratory scale
but the rates of phenol degradation under sonication have always
been quite low. Mahamuni and Pandit [3] used additives such as
salt and carbon tetrachloride with an aim of reduction in the treat-
ment times of phenol and hence the cost of operation.
Natural clay is also used as adsorbent for removal of organic
compounds from waste water such as dyes, humic acid, oil and
greases [4–6]. Several authors [7–10] showed that the ultrasonic
irradiation can oxidize various organic pollutants by the radical
reactions. Furthermore, the degradation of aqueous organic com-
pounds by photo-catalyst such as TiO2 was investigated under
influence of ultrasonic irradiations [11–13].
In this work, three different types of organically modified nano-
clay were synthesized using ultrasound. Each micron size particle
contains 1000 or more platelets, the gallery spacing between these
platelets increased by intercalation. The effect of different interca-
lating agents on adsorption of phenol in presence of ultrasound
* Corresponding author. Tel.: +91 20 24202124; fax: +91 20 24280926.
E-mail address: shirishsonawane@rediffmail.com (S. Sonawane).
experimental data into Freundlich and Langmuir models.
2. Experimental
2.1. Materials and methods
Natural bentonite was procured from Ganatra Mines (Jaipur, In-
dia). TBAC, CTAB, HDTMA were procured from Sigma Aldrich. Phe-
nol was procured from SD fine chem Mumbai, India and no further
purification was carried out.
2.2. Nanoclay synthesis
The bentonite sample was ground and sieved by 200-mesh then
washed with demineralized water for 3–4 times. Silica and Iron oxi-
des were removed by differential sedimentation technique. The
mixture was stirred for 1 h and then kept undisturbed overnight.
After filtration, the solid was exposed to slow evaporation, till the
desired dryness was obtained. An alkyl ammonium salt with long
chain (TBAC, CTAB and HDTMA) was selected as surfactant to widen
gallery spacing between platelets. To prepare the nanoclay, benton-
ite was treated with salts according to the following procedures.
2.2.1. Synthesis of TBAC and CTAB, HDTMA modified nanoclay under
sonication
TBAC, 2.77 g (calculated on the basis of CEC of bentonite used)
was dissolved in 75 ml of distilled water containing
3.90  103 g mol of hydrochloric acid. The mixture was stirred

1350-4177/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2008.03.006
1034 S. Sonawane et al. / Ultrasonics Sonochemistry 15 (2008) 1033–1037

under sonication at 80 °C during 30 min until a clear solution was
obtained, thus indicating a perfect dissolution of ammonium salt.
3.25 g of bentonite (CEC is 72 meq/100 g) was added to salt solu-
tion and sonication was continued for another 1.5 h. The precipi-
tate formed was recovered by filtration and dispersed in hot
water by mechanical stirring during 1 h. The later process was re-
peated twice to get chloride free nanoclay. The final precipitate
was thoroughly dried in an oven at 80 °C for 24 h to obtain the
TBAC modified nanoclay.
The procedure of synthesis of CTAB and HDTMA nanoclay is
similar as above; only quantity of CTAB (3.64 g) and HDTMA
(3.25 g) was changed depending on exchangeable ion content.
2.3. Adsorption experiments in sonication environment
2.3.1. Apparatus and procedure
Sono-sorption batch experiments were performed using ultra-
sonic bath with frequency of 22.5 kHz and a nominal power of
120 Watt (ULTRASONICS LABLINE CL 500). The bath has dimen-
sions 15  15  15 cm3. The total acoustic power injected into
the sample was calculated using calorimetric method. Calorimetric
method is generally used to determine the energy efficiency of the
equipment [14]. In this method rise in temperature of fixed quan-
tity of water in an insulated container over a given time was mea-
sured. Using this information, the actual power dissipated into a
liquid can be calculated from Eq. (1),
PowerðwattÞ ¼ mC p ðdT=dtÞ
gion of 500–4000 cm1 (Fig. 1). The characteristic peaks of benton-
ite, exchanged bentonite and their vibration frequencies were
obtained from literature [15–18].
The Infrared peaks obtained below the region of 200–500 cm1
are not taken in consideration, because they are assigned to mica.
Bentonite contains mica and presence of mica does not affect the
intercalation and source of bentonite remains unaffected in the
IR region [19]. FTIR spectra of bentonite and three organoclays
were shown in Fig. 1. The peaks between 3600 and 3700 cm1
are attributed to montmorillonite-rich smectite clay. Peaks at
3220 cm1 indicates N–H stretching. The significant peaks at
2940 and 2850 cm1 for all three modified nanoclays, are ascribed
to the asymmetric and symmetric vibration of methylene groups
(CH2)n of aliphatic carbon chain. Sharp peaks are observed in CTAB
and HDTMA modified nanoclay, while in case of TBAC modified
nanoclay are not pronounced, at 2850–2940 cm1, because the
CTAB and HDTMA are highly polar than TBAC. IR peaks at 915
and 836 cm1 represent the AlAlOH and AlMgOH bending vibra-
tions, respectively. The FTIR studies investigate the formation of
organic–inorganic hybrids (i.e. modified nanoclays). The results
ð1Þ

where Cp is the heat capacity of the solvent (J kg1 K1), m the mass
of solvent (kg), dT the difference between the initial and final tem-
perature after a specific reaction time (K) and dt is time (s). Using
this equation it was found the energy dissipated for sonication
was found 1.48 W/cm2 for present system.
The stock solution of phenol was prepared (10 g/l) and further di-
luted to desired concentrations. A 500 ml beaker containing 100 ml
phenol solution was located in the ultrasonic bath. The initial phenol
concentration was taken in the range of 250–5000 mg/l. The solu-
tion containing phenol and nanoclay was irradiated for 10 min and
1 h to reach equilibrium. The temperature of the bath was main-
tained constant using water circulation at room temperature.

2.4. X-ray diffraction spectroscopy and FTIR, TEM, UV spectroscopic

analysis

Powder XRD grams of natural bentonite clay and nanoclay were

recorded by means of X-ray diffractometer (Philips PW 1800). The
Cu Ka radiation (LFF tube 35 kV, 50 mA) was selected for the analy-
sis, by operating with an automatic divergence slit (irradiated sam-
ple length of 10 mm), a graphite monochromator and APD 1700
version 4.0 software. Fourier transform infrared ray (FTIR) spectro-
scopic measurement was performed using KBr pellets (2 mg/
300 mg KBr) on a spectrometer (Model 580, Perkin–Elmer) with a
resolution of 4.00 cm1. Infrared spectra were recorded in the range
4000–400 cm1. Transmission electron microscopy (TEM) image
was taken on a Philips Tecnai 20 model, which has resolution of
2 Å unit and Acc Voltage 200 kV with magnification of 7,50,000.
Phenol concentration was determined by using UV–VIS spectro-
photometer (SHIMADZU 160A model) at ambient temperature. The
wavelength of maximum absorbance (kmax) of phenol was 269 nm.
Demineralized water was used as reference.

3. Results and discussion

The IR spectrums for all four compositions (Natural Bentonite,

CTAB, HDTMA, TBAC modified Nanoclay) were obtained in the re- Fig. 1. FTIR spectra of natural clay and modified nanoclays.
 S. Sonawane et al. / Ultrasonics Sonochemistry 15 (2008) 1033–1037 1035

of FTIR further conformed using TEM image (Fig. 2), which shows
cross section of the CTAB nanoclay platelets. The nanometric
length of the nanoclay was found in the range of 30–50 nm.
X-ray diffraction patterns of natural and modified forms of clay
are reported in Fig. 3. It was found that intercalation of three differ-
ent intercalating agents, modify the crystal structure. Unmodified
bentonite has shown major peaks in the region of 2–5, the inten-
sity of peaks was in the range of 400–1000 cps. After the intercala-
tion of TBAC, nanoclay showed the amorphous nature in
comparison to the unmodified bentonite (Fig. 3A and C). In case
of TBAC modified nanoclay, the X-ray diffractrogram was below
the unmodified bentonite and area under the curve was found to
be increased, which indicate that the platelets were separated from
each other and TBAC modified nanoclay shows exfoliation behav-
ior. In case of HDTMA, CTAB modified nanoclay, XRD grams are
above the unmodified bentonite and area under curve is less in
comparison to the unmodified bentonite, it means that nanoclay
is found to become more crystalline in comparison to unmodified
bentonite. It shows the intercalating behavior of the salts and the
platelets are not fully separated from tactoids. It was found that
method of synthesis has effect on adsorbed quantity and equilib-
rium. With Phenol concentration of 2000 mg/l, it was found that,
if stirring is used for synthesis, adsorption was 37%, while
sonochemical synthesized clay shows 50% adsorption and also
ion exchange reaction time was found reduced in ultrasound
environment.
When higher concentrations of phenol were irradiated under
ultrasound, three nanoclay show that the equilibrium can be
achieved within short period of time (10 min). The time versus
concentration data has supplied in Fig. 4. In absence of ultrasound,
the time required to reach the equilibrium was found to be 45 min
for unmodified clay and 40 min for all three modified nanoclays. In
presence of ultrasound the equilibrium reaches within 15 min for
unmodified clay as adsorbent.
Fig. 5 shows the effect of different initial concentrations of phe- Fig. 3. XRD gram of natural clay and modified nanoclays.
nol, ranging from 250 to 5000 ppm. The mixture of phenol and
0.5 g clay was irradiated to ultrasound. It was found that with in-
crease in phenol concentration there is increase in adsorbed quan- shows that crystalline nature of TBAC nanoclay affects the adsorp-
tity of phenol. Initially, up to 2000 ppm all three nanoclay show the tion for higher range of phenol concentration. Due to sonication,
same adsorption. Further with increase in phenol concentration the TBAC modified clay gives more exfoliation; hence the satura-
adsorption increases in case of all three nanoclay, but it clearly tion comes at early stage, while crystalline CTAB, HDTMA modified

Fig. 2. TEM image of HDTMA modified nanoclay.

1036 S. Sonawane et al. / Ultrasonics Sonochemistry 15 (2008) 1033–1037

2000 0.45 TBAC modified clay

TBAC modified nanoclay

Phenol adsorbed per mg of clay

0.4 HDTMA modified clay
1800 CTAB modified nanoclay
0.35 CTAB modified clay
Concentration (ppm)

HDTMA modified
1600 nanoclay 0.3 Unmodified clay
unmodified nanoclay
0.25
1400
0.2
1200 0.15

0.1
1000
0.05
800 0
0 20 40 60 80 0 0.2 0.4 0.6 0.8 1 1.2
Time (min.) Clay quantity (g)

Fig. 4. Effect of sonication time on the phenol removal by nanoclays (C0 = 2000 p- Fig. 6. Phenol adsorbed on nanoclay at different loadings. (Initial phenol concen-
pm, 0.5 g clay). tration 2000 ppm.)

TBAC modified clay 1.2 y = 0.0121x + 0.5213

2500
R 2 = 0.82
HDTMA modified clay
1
CTAB modified clay
2000 0.8
Unmodified clay
Adsorbed conc. (ppm)

Ce/qe
0.6
1500
0.4

0.2
1000
0
0 10 20 30 40 50
500 Ce

Fig. 7. Langmuir adsorption isotherm for HDTMA modified nanoclay.

0
0 1000 2000 3000 4000 5000 6000
3.1. Isotherm models
Inital conc. of phenol (ppm)

Fig. 5. Effect of initial concentration on different adsorbents (clay quantity – 0.5 g).
nanoclay takes more time to get the phenol incorporated inside the
clay platelets, hence there is more diffusion resistance to pass the
phenol onto the nanoclay [20]. The TBAC is less polar than the
CTAB hence it affects the crystalline nature of the respective nano-
clay, thus amorphous TBAC modified nanoclay is found effective
than CTAB and HDTMA modified crystalline clays.
Fig. 6 shows the effect of clay loading onto the adsorption
capacity of nanoclay at 2000 ppm concentration of phenol. It is
found that with increase in clay quantity, phenol adsorbed onto
clay found to be decreased the behavior for all three types of nano-
clay show decrease in adsorption with increase in clay quantity. At
0.2 and 0.4 mg of clay, TBAC modified nanoclay shows less adsorp-
tion in comparison to CTAB and HDTMA modified nanoclay.
2000 ppm concentration of phenol is sufficient to reach the equi-
librium, hence cites for TBAC modified nanoclay were fulfilled with
phenol.
The linear plot of Ce/qe versus Ce had shown Langmuir isotherm
model for nanoclay sono-sorption (Fig. 7). The parameters, Qo and b
were determined from the slope and intercept of the plot and were
presented in Table 1. Qo is the maximum amount of phenol per unit
weight of the nanoclay to form complete monolayer on the surface
bound at higher Ce. Constant ‘b’ is related to the affinity to the
binding sites. For HDTMA modified nanoclay Qo value is 0.52 mg/
mg nanoclay and b value is 0.012 (Fig. 7). From R2 values, it is found
that all three nanoclay do not favor the monolayer Langmuir
adsorption isotherm. The reason behind that phenol is bulky mol-
ecule and the interlayer pores were not large enough to fully
accommodate the adsorbent.
Linear plot of log qe versus log Ce shown that the sono-sorption
follows Freundlich isotherm model for all modified nanoclays. k
and 1/n were calculated from the intercept and slope. For HDTMA
modified nanoclay (Fig. 8) the constants are 7.15 and 0.85 (slope
and intercept). The Freundlich intensity parameter, 1/n indicates
deviation of the adsorption isotherm from linearity. If 1/n = 1, the
adsorption is linear i.e. the adsorption sites are homogeneous

Table 1
The Freundlich and Langmuir parameters of adsorption isotherm models

Langmuir parameters Langmuir isotherm Freundlich parameters

TBAC HDTMA CTAB TBAC HDTMA CTAB
Qo (mg/mg) 0.53 0.52 0.49 Slope (1/n) 0.85 0.85 0.74
b (l/mg) 0.013 0.012 0.019 Intercept log k 0.30 0.30 0.38
Correlation coefficient (R2) 0.73 0.82 0.75 Correlation coefficient (R2) 0.96 0.97 0.95
 S. Sonawane et al. / Ultrasonics Sonochemistry 15 (2008) 1033–1037 1037

1.8 clay shows the endothermic in nature of heat of reaction, HDTMA

y = 0.8544x + 0.2996
1.6 modified clay shows higher value of heat of reaction (19.14 kJ/
R2 = 0.97
1.4 mol). It indicates that the temperature slightly above the ambient
1.2 would be favorable for carrying out the phenol adsorption under
ultrasound environment. Larger Qo values indicate that multilayer
log qe

1
adsorption for all the modified clays. The Gibbs free energy shows
0.8
the favorable adsorption in the following order, CTAB modified
0.6
clay < TBAC modified clay < HDTMA modified clay.
0.4
0.2
4. Conclusion
0
0 0.5 1 1.5 2
log ce Due to insertion of long chain quaternary salts the interlamellar
spacing of all three clay increases and sonication significantly re-
Fig. 8. Freundlich adsorption isotherm for HDTMA modified nanoclay. duces the synthesis time of nanoclay. Due to cavitation effect the
adsorption phenomena is found to be drastically improved and
Table 2
equilibrium is achieved within small period of time (10 min). It
Thermodynamic parameters for adsorption of phenol (2000 ppm) onto nanoclay (5 g/ seems that the diffusion resistance was overcome due to sonica-
L) after sonication of 1 h tion. The phenol adsorbed per mg of TBAC modified nanoclay is
Intercalating agent DH (kJ/mol) DS (J/mol K) DG (kJ/mol) at temperatures
higher (0.36 mg), at higher phenol concentration (5000 ppm). The
sonochemical sorption of phenol does not show monolayer adsorp-
308 K 319 K 329 K 338 K
tion. Freundlich adsorption isotherm favors for all three nanoclay,
CTAB 8.46 18.39 14.13 14.33 14.52 14.68 while HDTMA modified nanoclay shows higher 1/n and K value,
TBAC 10.71 25.93 18.69 18.98 19.24 19.47
HDTMA 19.14 24.84 26.79 27.06 27.31 27.54
HDTMA modified nanoclay shows higher adsorption capacity.
The Gibbs free energy shows the favorable adsorption for CTAB
modified clay.

and there is no interaction between the adsorbed sites. If 1/n is less
than 1, the adsorption is favorable; the adsorption capacity in-
creases and new adsorption sites appear. In HDTMA modified
nanoclay, sonication enhances the transport of phenol onto plate-
lets and the value of 1/n (0.8544) is less than 1, indicates favorable
adsorption. A similar trend was reported for the adsorption of phe-
nol and on dye onto bentonite [21,22], Acid blue 193 dyes onto Na
bentonite and HDTMA bentonite [23] and clay wood saw-dust
mixture [24].
3.2. Evaluation of thermodynamic parameters
Thermodynamic data such as adsorption free energy change,
considering the equilibrium constant, Ko, can be obtained from
the following equation:
DG0 ¼ RT ln K 0
0
Where DG is the free energy change (kJ/mol); R the universal gas
constant (8.314 J/mol K); K0 the thermodynamic equilibrium con-
stant and T the absolute temperature (K). Values of K0 may be cal-
culated from the relation ln qe/Ce versus. qe at different
temperatures and extrapolating to zero [25]. The corresponding val-
ues of DG0 are presented in Table 2. DG0 values were negative at all
investigated temperatures, indicating the spontaneous nature of
adsorption of phenol onto nanoclay. The values of DG0 obtained
were ranged from 14 to 27 kJ/mol, which indicates feasibility
of adsorption. The values of other thermal parameters such as en-
thalpy change (DH0), and entropy change (DS0), may be determined
from the Van’t Hoff equation, given below
ln K 0 ¼ DS0 =R þ DH0 =RT
0 0
DH and DG can be obtained from the slope and intercept of Van’t
Hoff plot of ln K0 versus 1/T. Positive values of DH0 further confirm
the endothermic nature of the adsorption process. All the modified
Acknowledgement
S.H. Sonawane is thankful to BCUD, University of Pune for
providing the financial support through Grant No. BCUD/578: 12-
Engg.
References
[1] R. Kidak, N.H. Ince, Ultrason. Sonochem. 13 (2006) 195.
[2] H. Nakui, K. Okitsu, Y. Maeda, R. Nishimura, Ultrason. Sonochem. 14 (2007)
191–196.
[3] N.N. Mahamuni, A.B. Pandit, Ultrason. Sonochem. 13 (2006) 165.
[4] M. Boufatit, H. Ait-Amarb, W.R. Mc Whinnie, Desalination 206 (2007) 394.
[5] M.S. El-Geundi, Adsorpt. Sci. Technol. 15 (1997) 777.
[6] R.S. Juang, S.H. Lin, C.H. Cheng, Ultrason. Sonochem. 13 (2006) 251.
[7] K. Kaikake, K. Hoaki, H. Sunada, R. Dhakal, Y. Baba, Bioresour. Technol. 98 (15)
(2007) 2787.
[8] K.S. Suslick, Proc. IEEE Ultrason. Symp. 1 (1997) 523.
ð2Þ [9] K.S. Suslick, D.A. Hammerton, R.E. Cline, J. Am. Chem. Soc. 108 (1986) 5641.
[10] N. Serpone, R. Terzian, P. Colarusso, C. Minero, E. Pelizzetti, H. Hidaka, Res.
Chem. Intermed. 18 (1992) 183.
[11] D.S. Bhatkhande, V.G. Pangarkar, A.A.C.M. Beenackers, J. Chem. Technol.
Biotechnol. 77 (2001) 102.
[12] C.D. Jaeger, A.J. Bard, J. Phys. Chem. 83 (1979) 3146.
[13] R.W. Matthews, J. Chem. Soc. Faraday Trans. 80 (1984) 457.
[14] P.R. Gogte, R.K. Tayal, A.B. Pandit, Curr. Sci. 91 (2006) 1.
[15] W.F. Moll, in: H. Van Olphen, J.J. Fripiat (Eds.), Data Handbook for Clay
Materials and Other Non-Metallic Minerals, Pergamon Press, Oxford, England,
1979.
[16] H. Slosiarikova, J. Bujdak, V. Hlauaty, J. Inclus. Phenom Mol. Recogn. Chem. 13
(3) (1992) 267.
[17] R.L. Ledoux, J.L. White, Science 145 (1964) 47.
[18] H.W. Van der Marcel, H. Beutel Spacher, Atlas of Infrared Spectroscopy of Clay
Minerals and Their Mixtures, Elsevier, Amsterdam, 1979. p. 275.
[19] S.D. Jang, A. Robert, American Minerologist 57 (1972) 494.
[20] M.M. Mortland, S.S. Stephen, M. Boyd, Clay Clay Miner. 34 (1986) 5 581.
[21] F. Banat, S. Al-Asheh, S. Al-Anbar, S. Al-Refaie, Bull. Eng. Geol. Environ. 66
ð3Þ
(2007) 53.
[22] F. Banat, A. Al Bashir, Al Aseh, O. Hayajneh, Environ. Pollut. 107 (2000) 390.
[23] A.S. Ozcan, B. Erdem, A. Ozacan, J. Colloid. Interf. Sci. 280 (2004) 44.
[24] N. Yeddou, A. Bensmaili, Desalination 185 (2005) 499.
[25] O. Abdelwahab, Desalination 222 (2008) 357–367.