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) for randomly
oriented powder samples. A step size of 0.02 (2 theta) was
used with a time of 1 s per step.
2.3.2 Surface area determination
Nitrogen adsorptiondesorption measurements were car-
ried out in liquid nitrogen temperature at 77 K using
NOVA 1000 Quantachrome (USA) for the analysis of BET
surface areas and pore size distribution. All samples were
preheated at 100 C for 2 h before the measurement.
2.3.3 Adsorption measurements
Gravimetric method was used for the measurement of
uptake of organic compounds and equilibrium adsorption.
McBain-Bakr gravimetric balance equipped with a sensi-
tive (25 cm/g) quartz spiral (Thermal Syndicate Ltd., UK).
A cathetometer with a precision of 0.001 cm was used
for measuring the spring extension. The details of the
adsorption system used in the study are reported elsewhere
[21]. Aromatic compound was degassed by freeze-pup-
thaw cycles before use. Vapour pressure of the com-
pound was determined with a pressure transducer (range
0100 Torr) from KS, USA. The adsorbent sample was
activated in situ at 150 C under vacuum (1 9 10
-5
Torr).
The sample was cooled to the desired temperature. The
aromatic hydrocarbons used in this study were obtained
from Aldrich Chemicals, USA.
2.3.4 Diffusion constant, D/r
2
The adsorption uptake data were used to calculate apparent
diffusivity, D/r
2
using the well known equation [22]
M
t
=M
1
1 6=p
2
X
1=n
2
expn
2
p
2
t D=r
2
where M
t
and M
?
are the amounts adsorbed at time t and
at innite time, respectively, r is the particle radius. D/r
2
was calculated by non-linear tting of the adsorption curve
to the solution of above equation.
3 Results and discussion
The amount of HDTMA sorbed between the montmoril-
lonite layers at different initial loadings, with respect to
CEC, of quaternary ammonium salt was measured by CHN
analyzer. The modied clays were found to retain increased
amounts of HDTMA as initial loadings of HDTMA
increased up to 2 CEC. Powder X-ray diffraction (XRD)
patterns of the clay material resulting from HDTMA and
nitron intercalation showed a clear swelling of the inter-
layers. The interlayer spacings of montmorillonite with and
without modication are reported in Table 1. HDTMA
added would locate themselves in the hydrophobic inter-
layer region resulting in the swelling of the clay layers.
Assuming that there is an increase of the basal spacing by
3.1 nm, for 2 lm clay particle size, there is a calculated
increase of the total pore volume by more than 10 times.
This also means that the space made available by swelling
is more than enough to accommodate 10 times the
observed amount of adsorbed HDTMA. The latter is
however restricted by the CEC even at higher loadings.
The HDTMA molecules in excess of CEC are weakly held
in the interlayer and get removed after washing. Formation
J Porous Mater (2010) 17:485490 487
1 3
of a bilayer would keep the clay layers apart with ample
free space in the interlayer.
3.1 Diffusivity in unmodied clay
Figure 1 presents the fractional uptake of benzene, toluene,
ethylbenzene and n-propylbenzene over unmodied
montmorillonite. The calculation based on this data
(Table 2) suggests the diffusivity (D/r
2
) to be in the order
benzene \toluene \ethylbenzene \n-propylbenzene.
Whatever adsorption that takes place on the unmodied
sample of clay, is outside the interlayer space where there
is no space restriction. The external surface of the clay
essentially consists of O and OH groups attached to tetra-
hedral silicate and also of the edges of the layers that form
this crystal. As the clay does not swell in hydrocarbons
they are not able to diffuse into the interlamellar space. The
diffusivity purely depends on the extent of interaction
between clay surface and aromatic molecules. Amount of
aromatic hydrocarbons adsorbed after 3600 s is reported in
Table 3. Amount of benzene adsorbed was highest and
n-propylbenzene was lowest, toluene and ethylbenzene
showed intermediate values.
3.2 Diffusivity in modied clay
The clay was modied to different extent by intercalating
HDTMABr, which resulted in varying interlamellar
spacing. The opening up of interlayer space enhanced the
length of diffusion path for the aromatic molecules in the
modied clay samples resulting in a decrease in diffusivity
(Table 2) as they have to now overcome the alkyl chains of
HDTMA occupying different locations in the interlamellar
region. Fractional uptake of aromatic hydrocarbons over
modied clay, montmorillonite-HDTMA-2CEC, is pre-
sented in Fig. 2. Table 3 depicts results of amount of
aromatics adsorbed on the modied clays after 3600 s.
These values are higher than that for unmodied clay
except in case of the aromatic having longer alkyl chain,
n-propylbenzene. One can easily make out the contribution
of interlamellar space towards adsorption by subtracting
unmodied clay adsorption values from the modied ones.
This contribution works out in case of montmorillonite-
HDTMA-2CEC to be almost three times that of unmodied
montmorillonite for the adsorbate benzene. Further the
contribution is two times for toluene and one time for
ethylbenzene, but almost the same for n-propylbenzene.
This is in line with size and shape of aromatic molecules.
3.3 Adsorption on zeolites and comparison with clays
In order to have an idea how the space available for dif-
fusion of aromatic molecules in the gallery of modied
clay is equivalent to system in which space is free of
HDTMA cation, the results have been compared with that
of zeolites 4A, ZSM-5 and beta. The rst zeolite has
channel dimension 3.8 9 4.0 A, the second one possesses
channel dimension 5.3 9 5.6 A, straight and zig-zag
channels intersecting each other, and last mentioned is a
large pore zeolite having three dimensional channel system
with dimension 6.0 9 7.3 A. Interesting feature about
these zeolites is 4A cannot adsorb inside its channels any of
the aromatic molecules we have studied, only they can get
adsorbed on the external surface sites, whereas, ZSM-5 and
beta can adsorb all of them. The results of adsorption of
benzene, toluene, ethylbenzene and n-propylbenzene on
4A, ZSM-5 and beta along with montmorillonite with and
without modications are presented in Table 4. Adsorption
Table 1 d(001) spacing and surface area of clay samples modied
with HDTMA and nitron
Clay sample Basal spacing,
d(001) (A)
Surface
area (m
2
/g)
Montmorillonite 9.5 21.0
Montmorillonite-HDTMA-0.5CEC 14.5 4.8
Montmorillonite-HDTMA-1CEC 18.2 3.5
Montmorillonite-HDTMA-2CEC 40.5 2.6
Montmorillonite-nitron 15.6 19.0
0.2
0.4
0.6
0.8
1
0 900 1800 2700 3600
Time, seconds
F
r
a
c
t
i
o
n
a
l
u
p
t
a
k
e
Benzene
Toluene
Ethylbenzene
n-Propylbenzene
Fig. 1 Fractional up take of aromatics over montmorillonite
Table 2 Diffusivity of aromatic hydrocarbons in montmorillonite
and montmorillonite-HDTMA-2CEC
Hydrocarbon Diffusivity (D/r
2
), s
-1
Montmorillonite
(untreated)
Montmorillonite-
HDTMA-2CEC
Benzene 7.40 9 10
-5
2.74 9 10
-5
Toluene 8.62 9 10
-5
7.10 9 10
-5
Ethylbenzene 1.08 9 10
-4
1.05 9 10
-4
n-Propylbenzene 1.22 9 10
-4
6.92 9 10
-5
488 J Porous Mater (2010) 17:485490
1 3
of benzene on montmorillonite-HDTMA-2CEC is more
than the three zeolites, while for toluene and ethylbenzene
it is in between that of ZSM-5 and beta zeolite. So, the
space available within the interlamellar space in modied
clay can be expressed in terms of zeolite channel space for
a specic adsorbate. Only one point we have not consid-
ered here is crystallite size variation of the zeolite. It is well
known that the diffusivity in zeolites is inuenced by the
crystallite size. Hence we are mentioning the crystallite
size of the zeolites used in our study, which is about 1lm.
3.4 Adsorption on nitron clay
Initially we started carrying out adsorption study to
understand our work on incorporation of a specic reagent
in the smectite clay (montmorillonite) to use it for trapping
a specic inorganic ion. As we could not achieve the
desired results it was decided to look at the interlayer space
of the clay after incorporation of organic reagent. Nitron
(Fig. 3), a specic reagent for nitrate ion (NO
3
-
) was
incorporated into the clay. XRD results conrmed inter-
calation of nitron in the clay. However, when nitronclay
was added to a solution containing NO
3
-
ion, it did not
reduce its concentration. It looks that Nitron is rmly held
in interlamellar region and is not able to interact with
NO
3
-
ion. Best way to nd out availability of space within
lamellar space is by carrying out adsorption study. It is
quite indicative from the results in Table 4 that nitronclay
has adsorption characteristic similar to unmodied clay.
That means though interlamellar space is opened up (basal
spacing 15.5 A from XRD) it is not accessible to benzene,
toluene or ethylbenzene. This can be explained based on
the fact that nitron is a bulky molecule containing three
phenyl groups and a ve membered heterocyclic ring
containing quaternary ammonium center, the latter has
entered the lamellar region partially and opened it up but
Table 3 Amount of aromatic hydrocarbons adsorbed on HDTMA-modied clays after 3600 s exposure
Clay sample Aromatic Hydrocarbon
Benzene (mmol/g) Toluene (mmol/g) Ethylbenzene (mmol/g) n-Propylbenzene (mmol/g)
Montmorillonite 1.483 0.838 1.116 0.554
Montmorillonite-HDTMA-1CEC 1.722 1.918 0.955 0.405
Montmorillonite-HDTMA-2CEC 5.574 2.539 2.060 0.562
0
0.2
0.4
0.6
0.8
1
0 900 1800 2700 3600
Time, seconds
F
r
a
c
t
i
o
n
a
l
u
p
t
a
k
e
Benzene
Toluene
Ethylbenzene
n-Propylbenzene
Fig. 2 Fractional up take of aromatics over montmorillonite-
HDTMA-2.0CEC
Table 4 Comparison of amount of aromatic hydrocarbons adsorbed on montmorillonite with and without modication and zeolites
Clay/zeolite Aromatic hydrocarbon
Benzene (mmol/g) Toluene (mmol/g) Ethylbenzene (mmol/g) n-Propylbenzene (mmol/g)
Montmorillonite 1.483 0.838 1.116 0.554
Montmorillonite-HDTMA-2CEC 5.574 2.539 2.060 0.562
Montmorillonite-nitron 1.168 0.625 0.975 0.619
4A 0.586 0.429 0.400 0.203
ZSM-5 1.779 1.359 1.536 0.853
Beta 4.354 3.912 4.007 2.108
Fig. 3 Structure of Nitron
J Porous Mater (2010) 17:485490 489
1 3
phenyl groups are not able to enter and hence has blocked
the accessibility completely. Redding et al. [2] observed a
similar blocking by benzyltriethyl ammonium ion for
benzene adsorption.
4 Summary
HDTMABr modied montmorillonite showed higher
adsorption capacity for benzene, toluene and ethylbenzene
than unmodied montmorillonite. The diffusivity
decreased on modication due to enhanced diffusion path
resulting from opening up of interlamellar space on inter-
calation. The space available within the interlamellar space
in modied montmorillonite can be expressed in terms of
zeolite channel space for a specic adsorbate. Adsorption
of benzene on montmorillonite-HDTMA-2CEC is more
than ZSM-5 and beta zeolite, while for toluene and ethyl-
benzene it is in between that of the two zeolites. Though
interlamellar space is opened up in case of nitronclay, it is
not accessible to benzene, toluene and ethylbenzene due to
complete blocking of space by the nitron. Adsorption of
organic compound of different size and shape is a good
technique to provide an insight into the interlamellar space
of organo-clay.
Acknowledgements YSB & BSJ would like to thank Principal and
Management of Bangalore Institute of Technology for the encour-
agement and facility to carry out this work. The authors express their
thanks to Department of Science & Technology, New Delhi for
nancial assistance. VRP and PK are thankful to Dr. A.B. Halgeri,
Head (R&D), Vadodara Manufacturing Division, RIL for continuous
encouragement and interest in the work. Authors are also thankful to
Mr. G.C. Patel for his assistance during experimental work.
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