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Journal of Membrane Science 354 (2010) 150–161

Contents lists available at ScienceDirect

Journal of Membrane Science

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

Mixed matrix blend membranes of poly(vinyl alcohol)–poly(vinyl pyrrolidone)

loaded with phosphomolybdic acid used in pervaporation dehydration of ethanol
Veeresh T. Magalad a , Gavisiddappa S. Gokavi a,∗ , K.V.S.N. Raju b , Tejraj M. Aminabhavi a,1
a
Department of Chemistry, Shivaji University, Kolhapur 416004, India
b
Organic Coatings and Polymers Division, Indian Institute of Chemical Technology, Hyderabad 500607, India

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

Article history: Mixed matrix blend membranes of poly(vinyl alcohol)–poly(vinyl pyrrolidone) (PVA–PVP) loaded with
Received 19 December 2009 4, 8 and 12 wt.% of phosphomolybdic acid (PMA) were prepared and characterized by FTIR, XRD, SEM,
Received in revised form 15 February 2010 DSC, dynamic mechanical testing analysis (DMTA) and contact angle measurements. The extent of PMA
Accepted 19 February 2010
loaded in the membrane affected the PV performance during ethanol dehydration. Selectivity calculated
Available online 25 February 2010
from permeability ratio of two components of a membrane was higher for 4 wt.% PMA-loaded mem-
brane than those of 8 and 12 wt.% loaded membranes. At the azeotropic mixture composition of 4% of
Keywords:
water and remaining ethanol, the 4 wt.% PMA-loaded membrane gave a selectivity of 8206 and a flux of
Pervaporation
Phosphomolybdic acid
3.75 g/m2 h kPa. Accordingly, this membrane was further investigated in detail to understand the effect
PVA–PVP blend of variations in feed water composition and temperature on its PV performance. Sorption and diffusion
Ethanol–water mixture results in conjunction with PV data were analyzed in terms of modified Flory–Huggins theory for three-
component system. Heat of sorption, calculated from Arrhenius relationship was negative, suggesting
Langmuir mode of sorption.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction membranes of PVA with other polymers [11–17]. PVP is another

Aqueous ethanol solutions are formed during the fermentation
of disposed biomass, wherein ethanol is used as a renewable source
of energy to replace conventional petroleum products. Purifica-
tion and concentration of aqueous ethanol in these processes are
generally carried out by distillation, but at azeotropic composi-
tion, the method is not efficient without recourse to benzene as an
entrainer, a deadly carcinogen. Alternatively, the membrane-based
pervaporation (PV) separation can be used to separate azeotropic
mixtures due to its intrinsic savings in capital and energy costs [1,2].
PV is thus an attractive method of separating azeotropic mixtures
[3–10]. In this study, mixed matrix membranes (MMMs) prepared
by loading different quantities of phosphomolybdic acid (PMA)
into the blend systems of poly(vinyl alcohol) (PVA) and poly(vinyl
pyrrolidone) (PVP) were used in the PV separation of water–ethanol
mixtures, and compared with the unfilled blend membrane.
In the literature, PVA has been widely used in PV dehydration of
organics [5] because of its good membrane forming ability, but its
excessive swelling in aqueous media tend to lower the selectivity
to water. In order to achieve its membrane stability and improve
selective characteristics, efforts have been made to develop blend
∗ Corresponding author. Tel.: +91 231 2609167; fax: +91 231 2692333.
E-mail address: gsgokavi@hotmail.com (G.S. Gokavi).
1
CSIR Emeritus Scientist, New Delhi, India.
important biopolymer used in PV dehydration studies [18]. In order
to improve PV separation characteristics of water–ethanol mix-
tures, in this work, blending of PVA with PVP is considered to limit
the excessive swelling of PVA. Since PVA and PVP polymers are
completely miscible in all proportions, due to hydrogen bond for-
mation between donor groups of PVA and acceptor groups of PVP,
in the blend system, it is thought that selectivity of PVA to water
might be enhanced thus, favoring dehydration of ethanol [19].
Apart from the above considerations and to attain better stabil-
ity of the membranes, efforts have been made to develop MMMs
by physical mixing of different types of inorganic fillers [20–23]. In
the past, phosphomolybdic acid (PMA) has been rarely chosen as a
filler [24,25]. PMA is a heteropolyacid, having one heteroatom sur-
rounded by four oxygens to form a tetrahedron. The heteroatom is
located centrally and caged by 12 octahedral MO6 -units linked to
one another by the neighboring oxygen atoms, thus with a total of
24 bridging oxygen atoms that link 12 addenda atoms. The metal
centers in the 12 octahedra are arranged in a spherical geometry,
almost equi-distant from each other, in four M3 O13 units, giving
an overall tetrahedral symmetry. The bridging and terminal oxy-
gen atoms on the periphery of the structure are thus available to
associate with water molecules to form hydrates that are thought
to enhance selectivity to water. Also, hydrogen-bonding is likely
to be established between PMA and PVA/PVP blend system. Hence,
in the present study, PMA-loaded PVA/PVP blend membranes are
fabricated and used in PV dehydration of ethanol.

0376-7388/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.02.055
 Author's personal copy
V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161
In all, four membranes were fabricated; of these, one was
unfilled nascent blend membrane of PVA/PVP and three were
MMMs prepared by incorporating 4, 8 and 12 wt.% of PMA into
the blend membranes of PVA/PVP, all prepared by solution cast-
ing method. Thus formed membranes were characterized by FTIR,
XRD, SEM, DSC, DMTA and contact angle measurements. The effect
of PMA content on swelling and PV performance was investigated
with reference to PV dehydration of ethanol. The results of this
study are analyzed by Flory–Huggins theory [30–32] extended
for three-component system. Sorption, diffusion and permeation
properties of the permeating liquids have been assessed in the
temperature interval from ambient (27 ◦ C) to 70 ◦ C. Arrhenius
parameters have been evaluated to discuss the data in terms of
temperature effects and also to understand the separation abilities
of the membranes over the range of temperature interval investi-
gated.
2. Experimental
2.1. Materials
Poly (vinyl pyrrolidone), (PVP), of weight average molecular
weight 40,000, was purchased from SRL, Mumbai, India. Poly
(vinyl alcohol), (PVA), of weight average molecular weight 125,000,
phosphomolybdic acid (PMA), glutaraldehyde and ethanol were
all purchased from s.d. Fine Chemicals, Mumbai, India. All the
chemicals were of reagent grade samples used without further
purification. Double-distilled water was used throughout the study.
2.2. Membrane preparation
PMA-filled blend membranes of PVA/PVP were prepared by
solution casting method by dissolving 6 g of PVA in 100 mL of dis-
tilled water at 90 ◦ C. Similarly, 6 wt.% of PVP solution was prepared
at ambient temperature (27 ◦ C) by mixing with PVA solution in the
ratio of 9:1 (volume basis) and stirring the mixture for 30 min to
form a homogeneous solution. After uniform mixing, the solution
was filtered to remove any suspended particles. In situ crosslink-
ing was done by adding 0.3 mL of glutaraldehyde (GA) to the above
solution and respective amounts (4, 8 and 12 wt.% with respect to
weight of the polymer) of PMA were added as catalyst for crosslink-
ing. The resulting solution was cast onto a clean glass plate in
a dust-free environment, the membranes obtained were dried at
ambient temperature and peeled off from the glass plate. Mem-
brane thickness was measured using a micrometer screw gauge and
was found to be around 50 ± 3 ␮m. Membranes were designated
as: M-0 (0.2 mL of conc. HCl as catalyst for crosslinking with pure
PVA and PVP blend system of 9:1 ratio); PMA-filled membranes
were prepared in the same manner by dispersing 4 wt.%, 8 wt.%, and
12 wt.% of PMA, designated as M-4, M-8 and M-12, respectively.
2.3. Membrane characterization
FTIR spectra of PMA, M-0, M-4, M-8 and M-12 were all scanned
in the range 400–4000 cm−1 using Nicolet, Impact-410 (Milwaukee,
WI), FTIR spectrophotometer by the KBr pellet method. A Siemens
D 5000 powder X-ray diffractometer was used to study the solid
state morphology of the membranes in powdered form. The X-rays
of 1.5406 Å wavelength were obtained by Cu K␣ radiation source.
Surface morphology of the membranes was obtained at 10 kV with a
JSM-840A scanning electron microscope (JEOL, Tokyo, Japan). Since
these films were non-conductive, gold coating of thickness 10 nm
was done on the samples. DSC thermograms were obtained using
SDT 2960 (TA Instruments, USA). Measurements were performed
at the heating rate of 10 ◦ C/min. The sample pan was conditioned in
the instrument before performing the actual experiment. Dynamic
151
mechanical testing analysis (DMTA) was done (Indian Institute
of Chemical Technology, Hyderabad) using Rheometric Scientific,
USA, DMTA IV instrument operated in a tensile mode at the fre-
quency of 1 Hz and at the heating rate of 6 ◦ C/min. Static contact
angles between water and membrane surfaces were measured
using contact anglemeter (Rame-hart, Model 500-F1, USA) at 25 ◦ C.
2.4. Swelling and sorption studies
Swelling experiments on the membranes were performed gravi-
metrically at 27 ◦ C in 10, 20, 30 and 40 wt.% water containing
feed mixtures. Initial masses of the circularly cut (dia = 3 cm)
membranes were taken by placing them on a single-pan digi-
tal microbalance (model AE 240, Mettler, Switzerland) sensitive
to ± 0.01 mg. Samples were placed inside the specially designed
airtight test bottles containing 30 cm3 of the test solvent and these
were kept in a hot-air oven maintained at a constant desired tem-
perature. Dry membranes were equilibrated by soaking in different
compositions of the feed mixture in a sealed vessel at 27 ◦ C for
48 h. Swollen membranes were weighed immediately after care-
fully blotting them on a digital single pan microbalance. The sorbed
liquids were recovered in a liquid nitrogen trap by desorbing the
equilibrated sample in the purge and trap apparatus, and analyz-
ing by gas chromatography (Model: Ultima-2100, Netel India Pvt.
Ltd., Mumbai, India). The percentage degree of swelling, DS was
calculated as:
W − W 
s d
Degree of swelling (%) = × 100 (1)
Wd
where Ws and Wd are the weights of the swollen and dry mem-
branes, respectively. Sorption selectivity, ˛s , was calculated as:
M   F 
w e
˛s = × (2)
Me Fw
where Mw and Me are the mass fraction of water and ethanol in
the membrane, Fw and Fe are those of water and ethanol in the
feed, respectively. Diffusion selectivity, ˛d , was calculated using
solution–diffusion theory [26]:
˛ij
˛d = (3)
˛s
where ˛ij and ˛S refer to real selectivity and sorption selectivity,
respectively. Considering the volatile nature of ethanol, all sorption
experiments were repeated thrice, but experimental errors were
within ±3%.
2.5. Pervaporation experiment
PV experiments were performed in an indigenously built appa-
ratus as described before [13]. Effective area of the membrane in the
PV cell was 26.43 cm2 with a liquid volume capacity of 200 cm3 . PV
apparatus was made of a stainless steel cell in which the feed stock
solution was maintained at the required constant temperature con-
trolled thermostatically with a water jacket. PV cell consists of an
efficient three-blade stirrer powered by DC motor in the feed com-
partment. Feed mixture was stirred at 3.334 Hz (200 rpm) speed by
maintaining the downstream pressure at 5 mbar using a vacuum
pump (Model: ED-21, Hindhivac, Bangalore, India).
Before starting the PV experiment, the test membrane was
equilibrated for 3 h with the feed mixture and after establish-
ment of steady state equilibrium, liquid permeate was collected
and condensed in traps under liquid nitrogen atmosphere. Per-
meate was collected up to 8–10 h and tests were carried out at
the required constant temperature. The collected permeate was
weighed after allowing it to attain the ambient temperature using
a digital microbalance sensitive to ±0.01 mg and was then ana-
lyzed by gas chromatography (Model: Ultima-2100, Netel India,
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152 V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161

Ltd., Mumbai) to calculate permeation rate, J and selectivity, ˛ij . It calculated as:
may be noted that in all our PV experiments, even after continu- P   F 
w o
ously using the present membranes for up to 8 h, they remained ˇij = × (14)
Po Fw
in-tact without showing any damage and hence, the same mem-
branes were used for repeated PV runs. where Pw and Po are wt.% of water and ethanol in permeate, Fw and
Permeation rate or flux (J) of water (w) and ethanol (e) were Fo are wt.% of water and ethanol in feed, respectively. Separation
calculated as per the theory of Wijmans and Baker [26]: factor does not reflect the real property of a membrane in many
Pi situations. In order to facilitate readers, we have also presented
p
Jw = (pfi − pi ) (4) both the sets of data, but discuss our results mainly based on real
l
selectivity, since it reveals the real effect of the amount of PMA
p Pj loading on membrane property.
Je = (pfj − pj ) (5)
l
Here the superscripts, f and p refer to feed and permeate, respec- 2.6. Thermodynamic analysis
tively; pi and pj are partial vapor pressures of water and ethanol,
respectively; Pi and Pj are membrane permeability coefficients of Thermodynamic analysis of sorption in terms of PV performance
water and ethanol, respectively, which are the product of diffusion is attempted based on the Flory–Huggins theory [30] as suggested
(Dij ) and solubility coefficients (Sij ). Diffusion and solubility coef- before [33] for a three-component system (polymer in mixed liq-
ficients are calculated using the procedure described elsewhere uid media) using Gibbs free energy of mixing (Gmix ); a similar
[17]; l is thickness of the membrane, while Pi /l and Pj /l are the approach was also attempted earlier for PV analysis [32]. The equa-
permeances of water and ethanol, respectively. The relationship tion for sorption selectivity, ˛s of a three-component system is
between partial vapor pressure (pfij ), molar concentration of water given as:
(xi ), ethanol (xj ) and activity coefficients of the individual compo- ˚  v  V  ˚ 
1 1 1 2
nents of the feed mixture obtained from the van Laar Eq. (20) of ln˛S = ln − ln = −1 ln
this paper are given as ˚2 v2 V2 v2
 V1

pfi = xi i psi (6) − 12 (˚2 − ˚1 ) − 12 (v1 − v2 ) − ˚P 1P − 2P (15)
V2
pfj = xj j psj (7) Here ˚i is volume fraction of the ith-component in the swollen
polymer membrane, vi is volume fraction of the ith component in
Saturated vapor pressures of water (psi ),
ethanol (psj )
were cal-
the external liquid phase and Vi is the respective molar volume(s).
culated using the Antoine equation [27] given in the form:
Subscripts 1, 2 and P refer, respectively to water, ethanol and poly-
A−B mer. The values of Vi at 27 ◦ C for water and ethanol were taken from
logpoij = (8)
T +C the literature [34], while volume fraction, P of the polymer in the
swollen state was calculated as [35]:
where poij are the vapor pressures of water and ethanol, respec-
tively; A, B, and C are Antoine constants were taken from the
 P
 M    −1
a P
literature [28], T is the temperature in Kelvin. By considering the ˚P = 1 + − (16)
S Mb S
activity coefficient and molar concentrations of individual com-
ponent, the saturated vapor pressure of water and ethanol were where P and S are the densities of polymer and solvent,
calculated: respectively; Mb and Ma are the masses of polymer before and
after swelling. Density of the polymer was measured by ben-
psi = xi i poi (9) zene displacement method using specific gravity bottle. Initially,
benzene-filled bottle and empty bottle weights were taken and a
psj = xj j poj (10)
weighed quantity of polymer was introduced into the bottle. Excess
Combining Eqs. (5)–(8), we obtain: benzene was wiped off with soft filter papers and mass of the bottle
P  along with benzene and polymer was taken. Volume of the polymer
i p was used to calculate density of the polymer; the molar volume of
Jw = (xi i psi − pi ) (11)
l water + ethanol mixture was calculated using [36]:
 
Pj p x1 M1 + x2 M2
Je = (xj j psj − pj ) (12) V= (17)
l m

In order to compute membrane selectivity, ˛ij , we prefer to use
the most recent paper of Baker et al. [29], according to which for
a binary mixture, selectivity is the permeability ratio of two com-
ponents of a membrane, an intrinsic property of the membrane,
under certain conditions or simply, it is the ratio of permeabilites
or permeances of components, i and j through the membrane and
is calculated as:
Pi /l
˛ij =
Pj /l
On the other hand, some authors use the separation factor
(ˇij ), calculated as the ratio of molar component concentrations
in the fluids on either side of the membrane. This quantity not only
depends on the selectivity of a membrane, but also on other param-
eters like feed composition and volatility of each component and is
where x1 , x2 are respectively, mole fractions of components 1 and 2
of the mixture, M1 , M2 are the corresponding molecular weights, m
is density of the water + ethanol mixture. The interaction parame-
ter, 12 between water and ethanol was calculated using [37]:
x1 ln(x1 /v1 ) + x2 ln(x2 /v2 ) + (GE /RT )
12 = (18)
x1 v2
where GE (J mol−1 ) is excess Gibbs free energy of mixing, R is
(13)
gas constant (J mol−1 K−1 ) and T is absolute temperature (Kelvin).
Values of GE were calculated using activity coefficients,  as:
GE = RT (x1 ln1 + x2 ln2 ) (19)
In the absence of direct experimental data on  1 and  2 , we have
used van Laar equation at 30 ◦ C to compute activity coefficient,  i
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V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161
Fig. 1. FTIR spectra of PMA, M-0, M-4, M-8 and M-12 membranes.
of component, i in the mixture as:
 2
Aji xj
lni = Aij
Aij xi + Aji xj
van Laar parameters, Aij for water and Aji for ethanol were taken
from the literature [28,38].
The polymer–solvent interaction parameter, iP was calculated
as [31]:
Vi (ıP − ıi )
2 for the separation, since it comprises of the hydrophilic–OH group.
iP =
RT
where ıi is solubility parameter of the ith component. Solubility
parameters of polymer, water and ethanol were taken from the
literature [34], but the solubility parameter, ı of the blend was
calculated using the additive relation [30]:
ı = w1 ı1 + w2 ı2
Here w1 and w2 are weight fractions, ı1 and ı2 are solubility param-
eters of PVA and PVP, respectively. These data were fed into Eq. (15)
to compute the sorption selectivity, ˛s .
3. Results and discussion
3.1. Characterization of membranes
3.1.1. FTIR studies
FTIR spectra of PMA and PMA-loaded blend membranes are
illustrated in Fig. 1. The spectrum of PMA shown in Fig. 1a
shows four characteristic bands (Keggin type) around 1064, 965,
868 and 785 cm−1 that are, respectively attributed to as (P–O),
as (Mo Ot ), as (Mo–Oc –Mo) and as (Mo–Oe –Mo) stretching
vibrations, wherein Ot , Oc and Oe refer to terminal, corner and
153
edge oxygens, respectively [39]. A strong and broad band appear-
ing around 3400 cm−1 corresponds to O–H stretching vibrations of
hydroxyl groups of PMA.
The spectrum of unfilled PVA–PVP blend membrane (M-0) and
those of the MMMs (i.e., M-4, M-8 and M-12) are displayed in
Fig. 1b. The M-0 membrane has characteristic peaks at 3440,
2900–2800, 1630 and 1020 cm−1 corresponding to peaks of –OH,
C–H, C O and C–O stretching vibrations, respectively. In case of M-
4, M-8 and M-12 membranes, no characteristic bands of Keggin unit
appeared, indicating homogeneous distribution of PMA particles
in PVA–PVP blend membranes [40]. For M-4, the peak inten-
sity corresponding to –OH around 3440 cm−1 shows a decrease
in intensity compared to unfilled M-0 membrane, indicating the
interaction between PMA and blend membrane through (Mo Ot ),
(Mo–Oc –Mo) and (Mo–Oe –Mo) (see Fig. 2). With the progressive
increase in PMA as in the case of M-8 and M-12, the peak intensity
of–OH becomes higher than that of M-4, due to large number of
hydroxyl groups of PMA.
3.1.2. XRD studies
The microstructure of PVA–PVP blend membrane along with
MMMs was studied by XRD. In this study, dried samples of 50 ␮m
thickness were used. Fig. 3 displays the XRD patterns of the dried
samples of M-0, M-4, M-8 and M-12. From the spectra, a moderately
sharp peak can be noticed for M-0 around 14◦ of 2, indicating its
semi-crystalline nature, whereas all the XRDs for MMMs showed
broad peaks with diminishing intensities at increasing loadings of
PMA particles; this also indicates the average intermolecular dis-
tance of the amorphous part of the matrix around 14◦ of 2. On the
other hand, relatively sharp intensity peaks are seen at 2 of 20◦ ,
indicating the existence of higher free volume in the unfilled blend
membrane (M-0), which would give a decrease in selectivity with
an increase of flux [41]. Thus, interactions of PMA with the poly-
mer blend seem to hinder the ordered packing of polymeric chains,
resulting in a reduced crystallinity of the blend. The loss of crys-
tallinity due to the addition of PMA is evident in Fig. 3, wherein a
(20)
progressive decrease in peak intensity is observed from 12 wt.% to
4 wt.% PMA loadings; this supports the observed improvement in
selectivity as the PMA loadings are lowered. As observed in Fig. 3
that there are two peaks one at 14◦ of 2 and another at 2 of 20◦ ,
which are related to two types of crystals: crystal 1 and crystal 2. Of
these, crystal 1, corresponding to peak at 14◦ of 2, is responsible
(21)
3.1.3. Scanning electron microscopy
SEM pictures of PVA–PVP mixed matrix membranes contain-
ing 4, 8 and 12 wt.% PMA were taken to inspect the distribution
of PMA particles. As can be seen from Fig. 4a–c, specially in the
case of M-4 membrane, we observe a smooth surface with uniform
(22) distribution of PMA particles. Such a homogenous mixing of PMA
particles in the bulk of the polymer phase would facilitate higher
water transport through the membrane due to the creation of chan-
nels that are more favorable to the transport of water molecules
than ethanol. With increasing loading of PMA, as in M-8 and M-12
membranes, some surface roughness can be seen, but with not so
much of uniform distribution of PMA particles on the surfaces of
the membranes.
3.1.4. DSC analysis
From the DSC curves of the unfilled (M-0) and filled (M-4, M-
8 and M-12) matrix membranes shown in Fig. 5, we find that
M-0 has a Tg of 82.3 ◦ C, which is shifted to higher temperatures
of 83.9◦ , 98.3◦ and 102.7 ◦ C for M-4, M-8 and M-12, respectively
after the addition of PMA; this can be attributed to intermolecu-
lar hydrogen-bonding interactions between the blend polymer and
the PMA particles. This would decrease molecular chain mobility
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154 V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161
Fig. 2. Schematics of the interaction between PMA and PVA–PVP blend.
of PVA–PVP polymer with increasing PMA loading. Notice that Tg
values of M-0 and M-4 membranes are quite identical, indicating
the compatibility between organic and inorganic phases, whereas
Tg of M-8 and M-12 are considerably higher than M-0 due to the
micro-phase separation during the membrane formation process
at >4 wt.% loading [42].
Fig. 3. XRD curves of M-0, M-4, M-8 and M-12 membranes.
3.1.5. DMTA analysis
DMTA measurements give information about the micro-
structural as well as thermal and viscoelastic properties of the
polymeric systems over a wide temperature interval. In DMTA,
EI represents the energy stored and recovered per cycle. The loss
modulus, EII measures the energy dissipated per cycle during defor-
mation. The ratio EII /EI is loss tangent. The tan ı of DMTA curves
shown in Figs. 6–8 suggest that with increasing PMA content, a
shift of tan ı peak at higher temperature occurs, such that higher
storage modulus is evident in the rubbery region. This behavior is
attributed to an impediment of the polymeric segmental motion
induced due to the presence of PMA particles. The observed EI
for M-0 at 35 ◦ C is 1.6 × 102 N/cm2 (1.6 × 107 dynes/cm2 ), which
got enhanced to 7.9 × 104 N/cm2 (7.9 × 109 dynes/cm2 ) after incor-
porating PMA (4 wt.%) into the blend. However, incorporation of
higher amount of PMA increased EI values, but the observed val-
ues for MMMs are quite higher than the unfilled (M-0) membrane.
It is certain that introduction of PMA particles between polymeric
chains would reduce the polymer chain mobility with a consequent
increase in its modulus. Such an increase in modulus gives reduced
free volume in the matrix.
3.1.6. Contact angle measurement
In PV separation, the surface free energy of the membrane is
important to understand the transport process, since surface free
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V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161 155

Fig. 5. DSC thermograms of M-0, M-4, M-8 and M-12, membranes.

Fig. 6. Temperature dependence of loss modulus (EII ) for M-0, M-4, M-8 and M-12
membranes.

3.2. Pervaporation performance

3.2.1. Effect of filler particles

Fig. 10 displays flux of water, ethanol and water selectivity cal-
culated using Eqs. (11)–(13) at 27 ◦ C for all the membranes at the
azeotropic composition i.e., 4 wt.% water plus remaining ethanol.
Initially, selectivity of 4 wt.% PMA-containing membrane (i.e., M-
4) increased considerably compared to nascent (M-0) membrane.
However, at higher concentrations of PMA i.e., M-8 and M-12 mem-

Fig. 4. Surface SEM images of (a) M-4, (b) M-8 and (c) M-12 membranes.

energy determines the surface and interfacial behavior in wetting

and adhesion. Even though surface energy cannot be measured
directly, few indirect methods have been proposed, of which use
of contact angle measurement of liquid and membrane surface has
been done in this study. Contact angle between water and mem-
brane surface gives a measure of membrane hydrophilicity; smaller
the contact angle, greater is its hydrophilicity. As shown in Fig. 9,
lower contact angle observed for M-0 than M-4, M-8 and M-12 indi-
cates that due to the presence of PMA particles in polymer phase,
hydrophilicity of the MMMs has changed. In this study, M-4 has
the highest contact angle at a lower concentration of PMA, sug-
gesting a reduction in hydroxyl groups of PVA of the blend. In the
presence of high PMA content, a large number of hydroxyl groups
tend to enhance the hydrophilicity of membranes, thus increasing
Fig. 7. Temperature dependence of dynamic storage modulus (EI ) for M-0, M-4, M-8
selectivity to water, with a concomitant decrease in water flux. and M-12 membranes.
 Author's personal copy
156 V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161
Fig. 8. Tan ı curves of M-0, M-4, M-8 and M-12 membranes.
Fig. 9. Effect of PMA content on contact angle between water and membranes.
branes, the selectivity values decreased considerably, but are still
higher than that observed for M-0. Such a rapid decrease in mem-
brane selectivity due to the addition of higher amounts of PMA
may be due to the change in pore texture of the membrane matrix
in the presence of PMA. This would also increase the void volume
of the membrane phase, a fact that was supported by water sorp-
tion/swelling studies as well as SEM images (Fig. 4) and contact
angle measurements (Fig. 9). Initially, the high density of functional
groups dominated the PV performance, but at certain concentration
of PMA in the membrane phase (viz., at 4 wt.%), the PV performance
becomes optimal. In this work, we have decided to investigate in
more details on M-4 membrane that gave the optimum selectivity
compared to all the membranes.
As regards flux of water for M-4 membrane, it is lower than those
observed for nascent (M-0) as well as M-8 and M-12 membranes,
but the flux curve for ethanol is independent of PMA loading and
the values are much lower than those observed for water as well
as follow the linear trend. An achievement of trade-off between
flux and selectivity has been a formidable task even though, it is
evident from Fig. 10 that both M-8 and M-12 membranes exhibit
lower selectivity and higher fluxes than M-4; this could be due to
the fact that linear polymer clusters in M-4 might have resulted
Table 1
Flux of water and ethanol, total flux, separation factor, selectivity, sorption and diffusion selectivities of different membranes at 27 ◦ C.
Membrane Jw (g/m2 h kPa) Je (g/m2 h kPa)
M-0 10.20 2.541
M-4 3.74 0.008
M-8 16.49 0.053
M-12 18.08 0.162
Fig. 10. Effect of PMA content on PV performance at azeotropic feed composition.
in high density of functional groups of PMA as per the interaction
model suggested in Fig. 2. Moreover, the resistance to molecular dif-
fusion and/or tortuosity of the diffusion pathway, resulting from the
lower degree of swelling does not change evidently when higher
amount of PMA particles are present in the membranes. Similar
results were observed by Wang et al., [42], who studied the clay-
modified polyimide/SDS-clay membrane for the PV separation of
water–ethanol mixture.
As per the principles of solution-diffusion [26], permeability
coefficient is the product of solubility and diffusivity. In order to
test this empirical hypothesis that is similar to gas transport pro-
cess [29], we have computed the values of sorption selectivity and
diffusion selectivity using Eqs. (2) and (3), respectively. These data
summarized in Table 1 suggest that sorption selectivity is much
higher than diffusion selectivity supporting the fact that more of
water molecules are transported through the membrane. It may be
noted that the values of ˇij calculated from Eq. (14), also included
in Table 1, display similar trends as those of ˛ij , but in general,
˛ij values are lower than those of ˇij . These data suggest that water
molecules are easily dissolved and transported into and through the
barrier membrane, resulting in an increase of sorption selectivity.
Consequently, sorption effect dominates the PV behavior, because
the real membrane selectivity follows the same trend as that of
sorption selectivity, but not diffusion selectivity. Here, of all the
membranes studied, M-4 exhibits higher sorption selectivity com-
pared to the remaining membranes and hence, M-4 was considered
for detailed studies on investigating the effect of temperature and
feed water composition on its PV performance.
3.2.2. Effect of feed water composition
In this study, PVP was considered for blending with PVA because
the rigidity and bulkiness of the derived blend membrane is as
important a factor as its hydrophilicity for an effective dehydra-
tion of ethanol. While hydrophilicity is needed for preferential
attraction of water to achieve high selectivity, the high rigidity
and bulkiness of the membrane are also equally necessary for an
easy transport of permeating water molecules. The performance of
nascent PVA/PVP blend membrane was investigated in comparison
to M-4 membrane as a function of feed water composition in order
Total flux (g/m2 h kPa) ˇij ˛ij ˛s ˛d
12.74 96 73 80 0.22
3.75 9,976 8,206 529 354
16.55 6,800 5,717 421 212
18.25 2,431 2,051 344 33
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V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161 157

Table 2
Effect of feed water composition on degree of swelling, flux of water and ethanol, total flux, separation factor and selectivity of M-0 and M-4 membranes at 27 ◦ C and 5 mbar
pressure.

Membrane Feed water composition (wt.%) DS (%) Jw (g/m2 h kPa) Je (g/m2 h kPa) Total flux (g/m2 h kPa) ˇij ˛ij

M-0 10 38 30.3 1.0 31.3 71 109

20 80 35.7 1.8 37.5 45 48
30 139 51.8 5.1 57.0 23 18
40 155 91.7 22.1 113.8 9 6

M-4 10 19 12.8 0.02 12.8 3,324 5,327

20 32 19.1 0.09 19.2 1,246 1,363
30 51 35.1 0.5 35.6 414 351
40 92 71.0 3.6 74.6 104 73

to show improved PV performance over that of the nascent (M-0)
membrane.
Table 2 displays the effect of feed water composition rang-
ing from 10 to 40 wt.% in the mixture on PV performance of
M-0 and M-4 membranes at 27 ◦ C under the constant pressure
of 5 mbar. For the unfilled M-0 membrane, percentage degree of
swelling is considerably higher than that observed for M-4. With
increasing feed water composition, for both the membranes (M-
0 and M-4), the percentage degree of swelling as well as flux
of water and ethanol both increased with increasing feed water
composition from 10 to 40 wt.% due to increased preferential inter-
action of water molecules with the membrane polymers. However,
extremely smaller values of flux are observed for ethanol compared
to water. Notice that total flux is almost close to the value observed
for water flux, indicating the water-selective nature of the mem-
brane. Conversely, selectivity decreased considerably for both the
membranes with increasing feed water composition. Particularly,
in case of M-0 (no filler), lower selectivity to water than M-4 is due
to the fact that blend polymer molecular segmental motion might
be retarded by the presence of PMA particles, resulting in a lesser
degree of swelling in M-4 than M-0 membrane. See for instance, the
highest selectivity of 5327 and separation factor of 3324 observed
for M-4 at 10 wt.% water-containing feed mixture, which is a clear
indication of the effect of added PMA particles into PVA/PVP blend
matrix. The decreased ˛ij and ˇij values with increasing water com-
positions of the feed mixture is due to the probable leaching of PMA
particles from the matrix polymer. Therefore, the present mem-
branes may not be extremely useful for separating aqueous ethanol
mixtures at higher amount of water.
It is likely that physico-chemical nature of the blend polymer
due to the presence of PMA particles might have changed. Het-
eropolyacids are like mineral acids having protons in the protected
environment, allowing them to interact with hydroxyl groups of
the blend polymer reducing the free volume channels in the bulk
of the polymer matrix, due to the reduction in degree of swelling.
There is also a possibility that with increasing feed water composi-
tion, more number of water molecules are sorbed by the filler PMA
particles due to induced plasticization effect of the membrane poly-
mer (even in the presence of small amount of ethanol) and also due
to increased chain mobility.
PMA is known to exhibit pseudo-liquid phase behavior, where
the polar water molecules will enter into the bulk phase by expand-
ing or contracting the distance between Keggin type anions in
the crystal lattice; thus, lesser number of ethanol molecules are
sorbed onto the membrane surface without actually entering into
the bulk due to H-bond formation between PMA protons and water
molecules that exist as guarded protons viz., H3 O+ or H5 O2 + [43,44].
With increasing feed water composition from 10 to 40 wt.%, more
of water molecules are replaced with lesser number of ethanol
molecules for protonation to take place. After protonation, ethanol
in the pseudo-liquid phase of PMA with its reduced size will perme-
ate through the membrane, thereby giving high flux with a reduced
selectivity. The present results demonstrate the positive role played
by the presence of PMA particles embedded into PVA–PVP blend
to enhance the membrane performance over that of the unfilled
PVA–PVP blend membrane.
3.2.3. Diffusion coefficient
Transport of binary liquid mixtures through PV membranes
can be conventionally explained by the solution-diffusion mech-
anism [26], which occurs in three steps: sorption, diffusion, and
evaporation. Permeation and selectivity are rather governed by
solubility and diffusivity of the components of the feed mix-
ture. Thus, in order to understand permeation, we have calculated
concentration-independent diffusion coefficient, Di of the perme-
ating molecules using Fick’s diffusion equation:
 dC 
i
Ji = −Di (23)
dx
where Ji is permeation flux/unit area (kg/m2 s), Di is diffusion coef-
ficient (m2 /s), Ci is concentration of permeate (kg/m3 ), subscript i
stands for water or ethanol, and x is diffusion path length. For sim-
plicity, we assume that concentration profile along the diffusion
pathway is linear and hence, concentration-independent, Di can be
calculated using:
Ji h
Di = (24)
Ci
where h is membrane thickness (50 ␮m in this study).
Calculated values of diffusion coefficients of water and ethanol
at temperatures between 40 ◦ C and 70 ◦ C are compiled in Table 3.
Notice that with increasing temperature from 40 ◦ C to 70 ◦ C, flux
of water as well as ethanol increased, but selectivity (˛ij ) as well
as separation factor (ˇij ) values decreased. The D values of water
are higher than those of ethanol by two orders of magnitude, fur-
ther signifying the water-selective nature of the membranes. It
is observed that diffusion coefficients of water as well as ethanol
increased systematically with increasing temperature, a trend that
follows the conventional Arrhenius trend.

Table 3
Effect of temperature on diffusion coefficients of water and ethanol, flux, separation factor and selectivity for M-4 membrane at 10 wt.% water containing mixture.

Temperature (◦ C) Dw × 108 (m2 /s) De × 1010 (m2 /s) Jw (g/m2 h kPa) Je (g/m2 h kPa) Total flux (g/m2 h kPa) ˇij ˛ij

40 4.9 3.4 7.9 0.13 8.04 366 577

50 6.4 6.2 28.7 0.26 28.95 262 412
60 10.9 13.9 53.6 0.66 54.29 197 311
70 14.5 21.6 81.2 1.16 82.38 169 265
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158 V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161

Table 4
Interaction parameters and sorption selectivity at different feed water compositions for M-4 membrane for water/ethanol mixture at 27 ◦ C.

Feed water composition (wt.%) Interaction parameters ˛s Expt. ˛s Cal.

Water/ethanol 12 Water/polymer 1p Ethanol/polymer 2p

10 1.61 0.020 2.48 110 116

20 1.36 0.018 1.23 34 35
30 1.19 0.017 0.80 12 14
40 1.05 0.015 0.68 6 7

3.2.4. Effect of temperature on pervaporation 2p values at all feed water compositions, due to water-selective
Temperature affects the PV performance. Flux increases with nature of M-4. Majority of water molecules are, therefore, adsorbed
increasing temperature, and hence, the overall temperature effect by the hydrophilic PMA particles, making it more water-selective,
on flux or diffusivity can be described through Arrhenius-type rela- thereby extracting more of water molecules on permeate side, thus
tionship, from which activation parameters can be computed. The enhancing the membrane selectivity to water. One can observe that
effect of temperature on PV performance was studied only in case of experimental and theoretical values of sorption selectivity are quite
M-4 membrane at a fixed feed water composition of 10 wt.% under comparable (see Table 4) and confirming that the proposed thermo-
5 mbar pressure. The temperature dependencies of permeation and dynamic treatment based on Flory–Huggins theory is satisfactory
diffusion have been investigated using the Arrhenius-type relation- to explain the PV results, and also, it gives accurate predictions.
ship:
 −E  3.4. Comparison of PV results with vapor–liquid equilibrium
a
X = Xo exp (25) (VLE) data
RT
where X represents the diffusion coefficient (D) or permeation flux As stated in the beginning of this paper, conventional distilla-
(Jp ), Xo is a constant representing the pre-exponential factors, Do or tion has drawbacks compared to the PV separation, particularly
Jo , and Ea represents the activation energy of permeation or diffu- for the separation of azeotropes and no complete separation can
sion and RT is the energy term. As the feed temperature increases, be achieved without adding an entrainer. To prove this anomaly,
vapor pressure in the feed side compartment increases, but vapor we have compared permeate concentration obtained in PV experi-
pressure on permeate side is not affected, resulting in increased ment for M-4 membrane with vapor–liquid equilibrium (VLE) curve
driving force. obtained from distillation [47] in Fig. 12. PV separation is thus a
Arrhenius plots of ln J vs 1000/T and ln D vs 1000/T shown, better option than distillation to break ethanol–water azeotropic
respectively in Fig. 11a and b for permeation flux and diffusion
exhibit linear trends, suggesting that permeability and diffusiv-
ity follow the Arrhenius rule. From the least squares fit of the
linear plots of Fig. 11a and b, activation energies of permeability
(Ep ) and diffusivity (Ed ) have been estimated. Permeation activa-
tion energy value of water (Epw ) obtained is 45.5 kJ/mol, which is
close to 46.4 kJ/mol found for total activation energy (Ep ), whereas
activation energy of ethanol (Epe ) is 69.15 kJ/mol, which is signifi-
cantly higher than Epw (45.5 kJ/mol). Diffusion activation energy of
water (Edw ) is 48.5 kJ/mol, while that of ethanol (Ede ) is 69.2 kJ/mol,
suggesting that both permeating and diffusing molecules require
higher activation energies for the molecular transport to take place
through the membrane. Notice that Ed values are higher than Ep
values, yet the difference is not significant, indicating that both per-
meation and diffusion would contribute to the overall PV process.
Using the values of Ep and Ed , heat of sorption, Hs was calcu-
lated as:

HS = Ep − Ed (26)

The resulting Hs is negative (−2.4 kJ/mol), which suggests that

the mode of transport involves contributions from Langmuir’s type
of sorption. Langmuir’s sorption requires the pre-existence of a
site in which sorption occurs by hole-filling mechanism giving an
exothermic contribution [45].

3.3. Thermodynamic interpretation

Experimental and theoretical values of sorption selectivity for

M-4 are given in Table 4. From the values of interaction param-
eters of M-4 calculated at different feed water compositions, we
see that the interaction parameter of water-membrane (1p ) and
ethanol-membrane (2p ) decreases with increasing feed water
composition. Usually, stronger interaction between the mixture
components would result in a smaller value of interaction parame-
ter [46]. In the present study, M-4 has lower 1p values and higher Fig. 11. Arrhenius plot (a) ln J vs. 1000/T and (b) ln D vs. 1000/T for M-4 membrane.
 Author's personal copy
V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161
Table 5
Comparison of flux and separation factor of the present mixed matrix membranes with literature for ethanol dehydration at 27 ◦ C.
Membrane Feed water composition (%)
Two ply composite CS/NaAlg 5.0
CS/NaAlg 13.5
P-NaAlg 5.2
CS 10.0
NaAlg 10.0
PVA/PVS 6.2
M-4 4.0
M-4 10.0
CS: Chitosan; NaAlg: sodium alginate; HEC: hydroxyethyl cellulose; P-NaAlg: phosphorylated sodium alginate; PVA/PVS: poly(vinylalcohol)/poly(styrene sulfuric acid).
composition, since here, the membrane acts as a third phase to
break such an azeotrope. Particularly, high selectivity of the mem-
brane would allow more of water molecules to transport across
the membrane due to its preferential affinity towards membrane,
thereby overcoming the azeotropic barrier.
3.5. Comparison of present data with literature
A number of studies have been made in the literature concern-
ing the PV separation of water–ethanol mixture. Therefore, it is
necessary to compare our data with those of the published reports.
Table 5 summarizes such data in comparison to the published
reports. However, a direct comparison of our PV data with litera-
ture findings is somewhat difficult, since such results are obtained
at varying feed water compositions and temperatures, yet some
data that are obtained under similar set of experimental conditions
for flux and separation factor are compared in Table 5 to assess the
usefulness of the present membranes with those of the published
reports.
In the case of M-4 membrane, for the separation of azeotropic
mixture, the highest separation factor of 9976 for water with a
lower flux of 0.10 kg/m2 h 10 ␮m is the result effect of added PMA
particles. In the case of novel composite chitosan membrane pre-
pared by Wang et al. [50], the separation factor is 8000, while
flux is 0.26 kg/m2 h 10 ␮m for 10 wt.% of water containing ethanol
feed. On the other hand, chitosan and sodium alginate blend mem-
brane [49] has a much lower separation factor of 436 and flux
Fig. 12. Comparison of vapor liquid equilibrium curve with PV data for
water–ethanol mixtures at 27 ◦ C.
159
ˇij J (kg/m2 h 10 ␮m) Reference
1,110 0.07 [48]
436 0.22 [49]
2,182 0.24 [2]
8,000 0.26 [50]
120 0.29 [51]
700 0.50 [52]
9,976 0.10 Present work
3,324 0.23 -do-
of 0.22 kg/m2 h 10 ␮m. The lowest value of separation factor of
120 is observed for pure NaAlg with a somewhat high flux of
0.29 kg/m2 h 10 ␮m [51]. Thus, overall, it can be inferred that after
the addition of PMA particles into the PVA–PVP blend matrix, one
can drastically increase membrane separation factor and/or selec-
tivity to water, but not flux.
4. Conclusions
It is demonstrated in this study that after incorporating 4 wt.%
of PMA particles into PVA–PVP blend matrix, one can enhance
the PV performance of the filled matrix membranes over that of
the unfilled PVA–PVP blend membrane during ethanol dehydra-
tion. However, higher loadings (8 and 12 wt.%) of PMA particles
did not result in any improvement of PV performance. Mem-
brane characterization by DSC and DMTA revealed an adequate
thermal and mechanical stability of the membranes, which is essen-
tial for PV dehydration above the ambient temperature. Sorption
selectivity of such membranes being much higher than diffusion
selectivity, favors the water separation selectivity during ethanol
dehydration, since the process is dominated by sorption mecha-
nism. Sorption selectivity of M-4 is higher than M-8 and M-12,
due to better compatibility of PMA particles into M-4 at 4 wt.%
loading than with M-8 and M-12. Selective sorption by the filler
particles increased the preferentially permeating water molecules
from ethanol-containing mixtures. Flory–Huggins theory enabled
the accurate predictions of the parameters and also the theory is
useful in satisfactorily explaining the thermodynamics of disso-
lution and permeation processes. With the increasing feed water
composition, membrane performance was affected markedly in
accordance with the swelling and flux data, which also supports
the fact that increase of selectivity and separation factor with a
reduction in flux. Azeotropic composition of water–ethanol mix-
ture was separated by the highly water-selective M-4 membrane,
which exhibited significantly lower activation energies for water
than ethanol, and with a negative heat of sorption, suggesting its
higher separation ability. Furthermore, sorption is dominated by
Langmuir’s mode of sorption. Finally, as suggested by one of the
referees, it may be useful to the compute real selectivity instead
of separation factor. However, in this work, we have explained our
data in terms of both selectivity and separation factor.
Acknowledgements
G.S.G. and V.T.M. thank Department of Science & Technology,
New Delhi, India (No. SR/S1/PC-31/2006) for a financial support.
T.M.A. thanks the CSIR, New Delhi, India [21/(0760)/09/EMR-II] for
awarding CSIR Emeritus Scientist. We also thank Profs. A.V. Rao and
P.S. Patil, Department of Physics, Shivaji University for providing
contact angle and SEM facilities. Finally, we immensely thank the
suggestion of an unknown reviewer to recast the PV data in terms
of real selectivity, which led to the novelty of this paper.
 Author's personal copy
160 V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161
Nomenclature
A effective membrane area (m2 )
J flux (kg/m2 h)
Jo pre-exponential factor for permeation
Ms and Md weights of the swollen and dry membranes
P and F weight% of permeate and feed
R gas constant
T temperature (K)
Wi weight of the permeate (kg)
Greek letters
˛d diffusion selectivity
˛ij real selectivity
˛s sorption selectivity
ˇij separation factor
ı solubility parameter
Hs heat of sorption (kJ/mol)
iP Flory–Huggins interaction parameter between sol-
vent and polymer
References
[1] S. Amnuaypanich, N. Kongchana, Natural rubber/polyacrylic acid semi-
interpenetrating polymer network membranes for the pervaporation of
water–ethanol mixtures, J. Appl. Polym. Sci. 114 (2009) 3509.
[2] S. Kalyani, B. Smitha, S. Sridhar, A. Krishnaiah, Pervaporation separation of
ethanol–water mixtures through sodium alginate membranes, Desalination
229 (2008) 68.
[3] T.M. Aminabhavi, R.S. Khinnavar, S.B. Harogoppad, U.S. Aithal, Q.T. Nguyen,
K.C. Hansen, Pervaporation separation of organic–aqueous and organic–organic
binary mixtures, J. Macromol. Sci. Rev. Macromol. Chem. Phys. C 34 (1994)
139.
[4] S.D. Bhat, T.M. Aminabhavi, Pervaporation separation using sodium alginate
and its modified membranes—a review, Sep. Purif. Rev. 36 (2007) 203.
[5] R.Y.M. Huang, Pervaporation Membrane Separation Processes, Elsevier Science
Publishers, Amsterdam, Netherlands, 1991.
[6] S.D. Bhat, N.N. Mallikarjuna, T.M. Aminabhavi, Microporous aluminophosphate
(AlPO4 -5) molecular sieve-loaded novel sodium alginate composite mem-
branes for pervaporation dehydration of aqueous–organic mixtures near their
azeotropic compositions, J. Membr. Sci. 282 (2006) 473.
[7] S.D. Bhat, T.M. Aminabhavi, Zeolite K-LTL-loaded sodium alginate mixed matrix
membranes for pervaporation dehydration of aqueous–organic mixtures, J.
Membr. Sci. 306 (2007) 173.
[8] J.H. Chen, Q.L. Liu, X.H. Zhang, Q.G. Zhang, Pervaporation and characterization of
chitosan membranes cross-linked by 3-aminopropyltriethoxysilane, J. Membr.
Sci. 292 (2007) 125.
[9] X.H. Zhang, Q.L. Liu, Y. Xiong, A.M. Zhu, Y. Chen, Q.G. Zhang, Pervaporation dehy-
dration of ethyl acetate/ethanol/water azeotrope using chitosan/poly(vinyl
pyrrolidone) blend membranes, J. Membr. Sci. 327 (2009) 274.
[10] Y. Ma, J. Wang, T. Tsuru, Pervaporation of water/ethanol mixtures through
microporous silica membranes, Sep. Purif. Tecnol. 66 (2009) 479.
[11] H. Zheng, Y. Du, J. Yu, R. Huang, L. Zang, Preparation and characterization
of chitosan/poly(vinyl alcohol) blend fibers, J. Appl. Polym. Sci. 80 (2001)
2558.
[12] B.V.K. Naidu, M. Sairam, K.S.V.N. Raju, T.M. Aminabhavi, Pervaporation of
water + IPA mixture using novel nanocomposite membranes of poly(vinyl alco-
hol) and polyaniline, J. Membr. Sci. 260 (2005) 131.
[13] T.M. Aminabhavi, H.G. Naik, Synthesis of graft copolymeric membranes of
poly(vinyl alcohol) and polyacrylamide for the pervaporation separation of
water/acetic acid mixtures, J. Appl. Polym. Sci. 83 (2002) 244.
[14] M.D. Kurkuri, U.S. Toti, T.M. Aminabhavi, Synthesis and characterization of
blend membranes of sodium alginate and poly(vinyl alcohol) for pervapora-
tion separation of water–isopropanol mixtures, J. Appl. Polym. Sci. 86 (2002)
3642.
[15] T.M. Aminabhavi, U.S. Toti, Pervaporation separation of water–acetic acid
mixtures using polymer membranes, Des. Monomers Polym. 6 (2003)
211.
[16] B.V.K. Naidu, S.D. Bhat, A.C. Wali, D.P. Sawant, N.N. Mallikarjuna, S.B. Hal-
ligudi, T.M. Aminabhavi, Comparative study on the pervaporation separation
of water + acetonitrile mixtures using zeolite-filled sodium alginate and poly-
(vinyl alcohol)–polyaniline IPN membranes, J. Appl. Polym. Sci. 96 (2004)
1968.
[17] S.G. Adoor, B. Prathab, L.S. Manjeshwar, T.M. Aminabhavi, Mixed matrix
membranes of sodium alginate and poly(vinyl alcohol) for pervaporation dehy-
dration of isopropanol at different temperatures, Polymer 48 (2007) 5417.
[18] J. Lu, Q.T. Nguyen, L. Zhou, B. Xu, Z. Ping, Study of the role of water in the
transport of water and THF through hydrophilic membranes by pervaporation,
J. Membr. Sci. 226 (2003) 135.
[19] Z.H. Ping, Q.T. Nguyen, J. Neel, Investigation of poly(vinyl alcohol) poly(n-vinyl-
2-pyrrolidone) blends. 3. Permeation properties of polymer blend membranes,
Macromol. Chem. Phys. 195 (1994) 2107.
[20] R. Mahajan, R. Burns, M. Schaeffer, W.J. Koros, Challenges in forming successful
mixed matrix membranes with rigid polymeric materials, J. Appl. Polym. Sci.
86 (2002) 881.
[21] Z. Huang, Y. Shi, R. Wen, Y. Guo, J. Su, T. Matsuura, Multilayer poly(vinyl
alcohol)–zeolite 4A composite membranes for ethanol dehydration by means
of pervaporation, Sep. Purif. Technol. 51 (2006) 126.
[22] Z. Huang, H. Guan, W. Tan, X. Qiao, S. Kulprathipanja, Pervaporation
study of aqueous ethanol solution through zeolite-incorporated multilayer
poly(vinyl alcohol) membranes: effect of zeolites, J. Membr. Sci. 276 (2006)
260.
[23] T.T. Moore, W.J. Koros, Non-ideal effects in organic–inorganic materials for gas
separation membranes, J. Mol. Struct. 739 (2005) 87.
[24] I.K. Song, S.K. Shin, W.Y. Lee, Catalytic activity of H3 PMo12 O40 blended poly-
sulfone film in the oxidation of ethanol to acetaldehyde, J. Catal. 144 (1993)
348.
[25] J.K. Lee, I.K. Song, W.Y.J. Lee, J. Kim, Modification of 12-molybdophosphoric acid
catalyst by blending with polysulfone and its catalytic activity for 2-propanol
conversion reaction, J. Mol. Catal. A 104 (1996) 311.
[26] J.G. Wijmans, R.W. Baker, The solution-diffusion model: a review, J. Membr. Sci.
107 (1995) 1.
[27] W.F. Guo, T.S. Chung, T. Matsuura, R. Wang, Y. Liu, Pervaporation study of water
and tert-butanol mixtures, J. Appl. Polym. Sci. 91 (2004) 4082.
[28] M.J. Holmes, M.V. Winkle, Prediction of ternary vapor–liquid equilibria from
binary data, Ind. Eng. Chem. 62 (1970) 21.
[29] R.W. Baker, J.G. Wijmans, Y. Huang, Permeability, permeance and selectivity: a
preferred way of reporting pervaporation performance data, J. Membr. Sci. 348
(2010) 346.
[30] B.V.K. Naidu, T.M. Aminabhavi, Pervaporation separation of water/2-propanol
mixtures by use of the blend membranes of sodium alginate and hydroxyethyl
cellulose: roles of permeate-membrane interactions, zeolite filling, and mem-
brane swelling, Ind. Eng. Chem. Res. 44 (2005) 7481.
[31] P.J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaca, New
York, 1953.
[32] T.M. Aminabhavi, P. Munk, Preferential adsorption onto polystyrene in mixed
solvent systems, Macromolecules 12 (1979) 607.
[33] M.H.V. Mulder, C.A. Smolders, On the mechanism of separation of
ethanol/water mixtures by pervaporation. Part I. Calculations of concentration
profiles, J. Membr. Sci. 17 (1984) 289.
[34] J. Brandrup, E.H. Immergut, E.A. Grulke, Polymer Hand Book,
Wiley/Interscience, New York, 1999.
[35] U.S. Aithal, T.M. Aminabhavi, P.E. Cassidy, Interactions of organic halides with
a polyurethane elastomer, J. Membr. Sci. 50 (1990) 225.
[36] M.I. Aralaguppi, T.M. Aminabhavi, R.H. Balundgi, S.S. Joshi, Thermodynamic
interactions in mixtures of bromoform with hydrocarbons, J. Phys. Chem. 95
(1991) 5299.
[37] T.M. Aminabhavi, P. Munk, Diffusion coefficients of some nonideal liquid mix-
tures, J. Phys. Chem. 84 (1980) 442.
[38] DECHEMA Chemistry Data Series by Gmehling, Onken, and Arlt., vol. 1, part 1b,
1977.
[39] G. Lakshminarayana, M. Nogami, Synthesis and characterization of pro-
ton conducting inorganic–organic hybrid nanocomposite membranes based
on tetraethoxysilane/trimethylphosphate/3 glycidoxypropyl trimethoxysi-
lane/heteropoly acids, Electrochim. Acta 54 (2009) 4731.
[40] J.H. Chen, Q.L. Liu, A.M. Zhu, Q.G. Zhang, J. Fang, Pervaporation separation
of MeOH/DMC mixtures using STA/CS hybrid membranes, J. Membr. Sci. 315
(2008) 74.
[41] K. Sunitha, Y.V.L. Ravi Kumar, S. Sridhar, Effect of PVP loading on pervapora-
tion performance of poly(vinyl alcohol) membranes for THF/water mixtures, J.
Mater. Sci. 44 (2009) 6280.
[42] Y. Wang, S. Fan, K.R. Lee, C.L. Li, S.H. Huang, H.A. Tsai, J.Y. Lai,
Polyamide/SDS-clay hybrid nanocomposite membrane application to
water–ethanol mixture pervaporation separation, J. Membr. Sci. 239 (2004)
219.
[43] S. Shanmugam, B. Vishwanathan, T.K. Varadarajan, Esterification by solid
catalysts—a comparison, J. Mol. Catal. A 223 (2004) 143.
[44] I.V. Kozhevnikov, Catalysis by heteropoly acids and multicomponent polyox-
ometalates in liquid-phase reactions, Chem. Rev. 98 (1998) 171.
[45] T.M. Aminabhavi, M.B. Patil, S.D. Bhat, A.B. Halgeri, R.P. Vijayalakshmi, P. Kumar,
Activated charcoal-loaded composite membranes of sodium alginate in perva-
poration separation of water–organic azeotropes, J. Appl. Polym. Sci. 113 (2009)
966.
[46] Q.G. Zhang, Q.L. Liu, Z.Y. Jiang, L.Y. Ye, X.H. Zhang, Effects of annealing on
the physico-chemical structure and permeation performance of novel hybrid
membranes of poly(vinyl alcohol)/␥-aminopropyl-triethoxysilane, Microp-
orous Mesoporous Mater. 110 (2008) 379.
[47] D. Bahrens, R. Eckermann (Eds.), Vapor–liquid Equilibrium Data Collection, vol.
1, Part 6C, DECHEMA, 1983.
[48] G.Y. Moon, R. Pal, R.Y.M. Huang, Novel two-ply composite membranes of chi-
tosan and sodium alginate for the pervaporation dehydration of isopropanol
and ethanol, J. Membr. Sci. 156 (1999) 17.
 Author's personal copy

V.T. Magalad et al. / Journal of Membrane Science 354 (2010) 150–161 161

[49] P. Kanti, K. Srigowri, J. Madhuri, B. Smitha, S. Sridhar, Dehydration of ethanol
through blend membranes of chitosan and sodium alginate by pervaporation,
Sep. Purif. Technol. 40 (2004) 259.
[50] X.P. Wang, Z.Q. Shen, Y.F. Zhang, Zhang, A novel composite chitosan mem-
brane for the separation of alcohol–water mixtures, J. Membr. Sci. 119 (1996)
191.
[51] C.K. Yeom, J.G. Jegal, K.H. Lee, Characterization of relaxation phenomena and
permeation behaviors in sodium alginate membrane during pervaporation sep-
aration of ethanol–water mixture, J. Appl. Polym. Sci. 62 (1996) 1561.
[52] A. Toutianoush, L. Krasemann, B. Tieke, Polyelectrolyte multilayer membranes
for pervaporation separation of alcohol/water mixtures, Colloids Surf. A 198
(2002) 881–889.