Journal of Membrane Science 274 (2006) 116122

Thermo-osmosis of mixtures of water and

methanol through a Nafion membrane
J.P.G. Villaluenga, B. Seoane, V.M. Barragan, C. Ruiz-Bauza
Department of Applied Physics I, University Complutense of Madrid, 28040 Madrid, Spain
Received 22 April 2005; received in revised form 15 June 2005; accepted 8 August 2005
Available online 22 September 2005

Abstract
Mass transport of mixtures of water and methanol through a Nafion membrane as a function of the temperature difference between the two sides
of the membrane was measured under different experimental conditions. The results show that the composition of the solutions, the temperature
difference across the membrane, and the mean temperature in the membrane cell are governing factors in the thermo-osmotic transport process. In
all cases studied, the thermo-osmotic flux through the membrane goes from the low temperature side to the high temperature side, and it increases
linearly with the temperature difference. Moreover, the flux also increases with the mean temperature in the membrane cell. The thermo-osmotic
coefficient of methanol in the membrane is higher than that of water. For water/methanol mixtures, the total flux through Nafion membrane can be
larger than the fluxes of pure solvents, and it increases with the methanol content for water/methanol mixtures.
2005 Elsevier B.V. All rights reserved.

Keywords: Nafion membrane; Water methanol mixtures; Thermo-osmosis

1. Introduction phane and weak charged cellulose acetate membranes using

If a membrane separates two solutions at different tempera-
tures, several transport processes through the membrane can be
observed. These phenomena are known as thermo-osmosis and
membrane distillation for solvent fluxes, and thermodialysis for
solute fluxes. Although the non-isothermal transport of fluids
has been known since the beginning of the twenty century, and
despite of its importance for some biological phenomena, they
have received comparatively less attention than the correspond-
ing isothermal effect. This is probably due to a lack of practical
application of thermo-osmosis, since small solvent fluxes and
small separations are normally obtained.
Most of the existing data in literature about thermo-osmosis
through charged membrane deal with aqueous electrolyte solu-
tions [18]. The results show that the direction of the flux
depends on the experimental conditions, although in general,
thermo-osmosis occurs toward the cold side for hydrophobic
membranes and toward the hot side for hydrophilic mem-
branes. Many studies have also been carried out with cello-
Corresponding author. Tel.: +34 91 394 51 91; fax: +34 91 394 51 91.
E-mail address: caruba@fis.ucm.es (C. Ruiz-Bauza).
non-electrolyte solutions [914], mainly with water or differ-
ent alcohols. In the last years, data referring to thermo-osmosis
are very scarce, and the studies about thermo-osmosis of non-
aqueous solution across highly charged membrane are practi-
cally inexistent.
Recently, the study of the transport phenomena in organic
media has reached special interest, mainly because its impor-
tance in the development of direct methanol fuel cells. Polyper-
fluorosulfonic acid Nafion membranes or their modifications
are commonly used as electrolyte in fuel cells, reason for
which this membrane are frequently used to study the transport
phenomena in non-aqueous media. Usually, fuel cells oper-
ate under isothermal conditions. However, temperature gradient
can be originated during the cell operation, affecting to the
water and thermal management, critical factors to the over-
all cell performance [1517]. For this reason, non-isothermal
fuel cells are being investigated [18,19]. In this sense, the
study of the non-isothermal transport across this kind of mem-
branes may be of great interest. In this work, the non-isothermal
transport of water, methanol, and mixtures of both liquids
have been studied. The present study had three main objec-
tives, namely to analyse the effect on the thermo-osmotic flux
of the composition of the solutions, the temperature differ-

0376-7388/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2005.08.010
 J.P.G. Villaluenga et al. / Journal of Membrane Science 274 (2006) 116122
ence across the membrane, and the mean temperature in the
cell.
2. Experimental
2.1. Materials
A commercial membrane Nafion 117 with a nominal equiv-
alent weight of 1100 g/equiv. was used in this study. Nafion 117
is a cation-exchange membrane consisted of a polytetrafluo-
roethylene backbone and regularly spaced perfluorovinylether
side chains terminated by sulfonate group. The perfluorinated
backbone is extremely high hydrophobic, whereas the sulfonic
groups are very high hydrophilic. In the presence of water, this
gives rise to some hydrophobic/hydrophilic separation. The sul-
fonic functional groups aggregate to form clusters, which are
connected by short channels. Other researchers have suggested
the presence of an intermediate region between the fluorocarbon
backbone and the hydrophilic domains.
The thickness, maximum water uptake and ion-exchange
capacity provided by the manufacturer for this membrane are
1.83 104 m, 35% and 1.13 kmol/m3 , respectively.
Pure pro-analysis grade methanol and bidistilled pure water
were used in the present study.
2.2. Apparatus
The thermo-osmosis unit used in the present study is sketched
in Fig. 1. The membrane cell consisted of two independent
chambers made of PTFE of approximately 104 m3 of volume
separated by the membrane. Each chamber was provided with
three orifices communicating to the exterior. In both chambers
Fig. 1. Sketch of the experimental device used in the experiments: M: membrane; CH: chamber cell; TP: temperature probe; C: capillary tube; B: mass balance; R:
solution reservoir; P: peristaltic pump; T: thermostat; TD: digital thermometer unit; TCS: ambient temperature control system.
117
a temperature probe was introduced in one of the orifices, so
the temperature was measured at a distance of 0.02 m from the
membrane. The other two orifices are used as solution inlet and
outlet.
The active area of the membrane was 25.2 104 m2 . Before
the experiments were carried out, the membrane was previously
boiled for 1 h in deionised and bidistilled water.
Two glass reservoirs of about 103 m3 of capacity were used
to contain the circulating solutions in both chambers. Each reser-
voir is provided with three orifices. Two orifices are used as
solution inlet and outlet. In order to avoid any pressure differ-
ence built-up between the reservoirs, one L-shaped capillary
tube was introduced in each reservoir, and they are kept at the
same height.
The temperature of the solutions contained in the reservoirs
was measured by means of a temperature probe connected to
a digital thermometer unit. In addition, each reservoir had a
jacket made of glass, where water was maintained at constant
temperature by means a circulation with a thermostat (Techne
TU-16D model). Moreover, one of the reservoirs was placed over
a mass balance (Sartorius BL3100 model), which permitted to
measure the mass change in the reservoir as a function of time.
The accuracy in the mass measurement was 0.1 g.
The complete unit was placed in a large ambient thermostat,
which was divided in two compartments by means of an appro-
priate wall. Each compartment contains one half-cell and the
corresponding reservoir. The temperature value in each com-
partment was maintained very close to the temperature of the
circulating solutions.
The temperature measurement both in the cell and in the
reservoirs was conducted by using an electronic device (Jenco
1671 model) with an accuracy of 0.1 C.
118 J.P.G. Villaluenga et al. / Journal of Membrane Science 274 (2006) 116122
Measurements were performed by using pure water, pure
methanol and mixtures of water and methanol with a
methanol content of 25, 50, and 75% (w/w), respectively. The
methanol/water solutions were previously degassed in order to
prevent the bubble formation during the measurement process.
The solutions were made to circulate between the reservoirs
and the cell by means of a peristaltic pump (Masterflex L/S
model. Cole-Parmer). The circulation velocity of the solutions
was varied between 100 and 400 cm3 /min.
2.3. Methods
At the beginning of the experiments, two water/methanol
solutions with the same composition were placed in the reser-
voirs. When the temperature of the solutions placed in each
reservoir reached the selected value, the solutions were made
to circulate through the cell, and the mass change was measured
as a function of time in the reservoir placed over the mass bal-
ance. Usually, this reservoir was used as the cold reservoir. The
mass flux through the membrane was determined from the slope
of plots of the mass change in this reservoir against time.
The temperature of the reservoirs, the temperature in the cell
at the two sides of the membrane, and the temperature in the
two compartments of the ambient thermostat were continuously
measured over the duration of each experiment, which was about
8 h. It should be noted that the temperature difference between
the two sides of the membrane was different from the tempera-
ture difference between the solutions in the reservoirs.
3. Results and discussion
3.1. Thermo-osmotic ux
Fig. 2 shows an example of the mass change of the cold
reservoir, and the temperatures in the cell at the two sides of the
membrane as a function of time when pure water was used. In this
case, the circulation velocity was 300 cm3 /min, the measured
temperature difference between the two sides of the membrane
was 8.8 C and the mean temperature in the membrane cell was
Fig. 2. Mass change in the cold reservoir, hot temperature and cold temperature
as a function of time. The solution used was pure water and the flow rate was
300 cm3 /min.
26.4 C. It is observed a decrease of the mass in the cold reser-
voir. The same behaviour was obtained in all the experiments
regardless the solution used. Therefore, it can be stated that the
direction of thermo-osmotic flux through the membrane goes
from the cold side to the hot side. In this case, the thermo-osmotic
flow is considered as positive. Thus, the solution is transferred
in the opposite direction in which thermal energy is transported,
which is a typical behaviour for cation-exchange membranes,
despite the fact that a non-electrolyte is used as solution. The
membrane behaviour is so as a hydrophilic membrane [5], which
is in accordance with the hypothesis that the transport is made
through the hydrophilic canals of the membrane. These results
are in agreement with the results obtained by other authors with
Nafion membranes using water [6].
In all the measurements, it is observed an initial stage in which
the temperature difference across the membrane cell is not con-
stant. Then, the temperature difference becomes constant, and a
linear dependence was observed of the mass change with time.
These findings seem to indicate that steady-state conditions pre-
vailed during the experiment after an initial transient period.
The transient behaviour may be due to a conditioning process
related to the adaptation of the membrane transport properties
to the rapidly changed operation conditions. This fact could be
explained in terms of the membrane swelling and deformation.
Moreover, it was observed that the duration of the transient
period was not constant, and there was not found any corre-
lation between the extension of this period and the experimental
conditions. The mass flux, J, through the Nafion membrane of
area A is calculated as follows:
1 dm
J= (1)
A dt
Thus, in each case, as it was noted above, the mass flux through
the membrane was estimated from the slope of the straight-line
m(t) in the steady-state region. The solid line in Fig. 2 corre-
sponds to this fitting.
The influence of the methanol percentage of the solutions on
the thermo-osmotic flow has been studied. Fig. 3 shows, as an
Fig. 3. Mass change in the cold reservoir as a function of time, at different weight
percentages of methanol in the solution. The temperature difference across the
membrane and the mean temperature in the cell were about 6.6 and 27.0 C,
respectively, and the solutions flow rate was 300 cm3 /min.
 J.P.G. Villaluenga et al. / Journal of Membrane Science 274 (2006) 116122 119

example, the mass change in the cold reservoir as a function of

time when solutions with different methanol content are used
in the measurements. In this case, the temperature difference
across the membrane and the mean temperature in the cell were
about 6.6 and 27.0 C, respectively. A decrease of the mass in
the cold reservoir was found in all cases studied, with a similar
behaviour to the one previously described for the case of pure
water. Moreover, for water/methanol mixtures, an increase of the
mass change was observed when the percentage of methanol in
the mixture increased.
It should be noted that the reproducibility of thermo-osmotic
flux was good, under given experimental conditions. The regres-
sion analysis of the mass data obtained with solutions with
different methanol percentages was carried out by the least-
square method. The correlation coefficients were equal to 0.98 Fig. 4. Effect of flow rate on the thermo-osmotic flux through the membrane.
The solution was a mixture of methanol/water 75/25% (w/w), the temperature
and higher. The continuous lines in Fig. 3 depict these linear fits.
difference was 9.7 C, and the mean temperature was 26.5 C.
One of the problems for obtaining reliable data of thermo-
osmosis is the measurement of the effective temperature differ-
elsewhere, which showed that the influence of the stirring rate
ence across the membrane. As it has been pointed out by several
is very small at velocities higher than 100 ml/min [3].
authors, the effective temperature on both sides of a membrane
Fig. 5 shows data of the thermo-osmotic flux as a function of
may be entirely different from the temperature difference in
the temperature difference across the membrane, when differ-
bulk solutions [4,20]. This effect, which is called temperature
ent water/methanol solutions are used. The mean temperature
polarization, is due to the existence of a stagnant liquid layer
was kept constant at 26.5 C in all cases. It is observed that the
adjacent to the membrane surface. In thermo-osmosis, the thick-
flux is lower for pure water than that for pure methanol. For
ness and the influence of this layer depend mainly on the thermal
water/methanol mixtures, at a given temperature difference, the
conductivity of the liquid solution and the membrane, as well
higher the methanol content, the higher the thermo-osmotic flux.
as the hydrodynamics conditions in the membrane cell. Dif-
It is also found that the total flux for mixtures with a 75% (w/w)
ferent studies [20,3] indicate that the temperature polarization
methanol content is larger than the flux for pure methanol.
effect decreases when the solution-stirring rate increases due
Fig. 6 shows the thermo-osmotic flux through the membrane
to a reduction in the thickness of the temperature polarization
as a function of the average temperature in the cell. The used
layers. In the present investigation, the temperature difference
solution was methanol/water 75/25% (w/w) and the measured
is measured by using probes placed very close to the mem-
temperature difference across the membrane was 9.7 C. It is
brane surfaces. Although such locations may exclude part of
found that the overall flux increases with increasing the mean
the temperature polarization, some of it will be present and its
temperature at a given temperature difference. These results are
contribution to the thermo-osmotic process cannot be neglected.
in agreement with the results obtained for other authors with
Consequently, it is important to note that in the present study
charged membranes [4]. The most appropriate way to describe
the temperature difference across the membrane is apparent, not
the data given in Fig. 6 is by means of an Arrhenius equation,
effective, and it will depend on the hydrodynamic conditions of
the system.
In order to analyse the temperature polarization effect, mea-
surements in different hydrodynamic conditions have been car-
ried out. In Fig. 4, the thermo-osmotic flux through the mem-
brane is presented as a function of the circulation velocity of the
solution in the range from 100 to 400 ml/min. In each case, the
solution was a mixture of methanol/water 75/25% (w/w), the
temperature difference was 9.7 C, and the mean temperature in
the cell was 26.5 C. It is readily observed that the values for the
flux are not affected by the solution flow rate within experimen-
tal accuracy. Such behaviour was found in all cases regardless
the composition of the solution used in the measurements. This
fact seems to indicate that although the temperature polariza-
tion effect can never be completely neglected, its quantitative
influence can be considered negligible under the experimental
conditions and within the experimental error. Thus, the ratio
Fig. 5. Thermo-osmotic flux of water/methanol mixtures as a function of the
between the temperature difference in the membrane,
T, and temperature difference across the membrane at different methanol weight per-
in the bulk,
Tb , can be considered practically the unity. On the centages. The circulation velocity was 300 cm3 /min, and the mean temperature
other hand, these results are in accordance with data published was 26.5 C.
120 J.P.G. Villaluenga et al. / Journal of Membrane Science 274 (2006) 116122
Fig. 6. Effect of mean temperature in the membrane cell on the thermo-osmotic
flux. The solution was a mixture of methanol/water 75/25% (w/w), the circula-
tion velocity was 300 cm3 /min, and the temperature difference was 9.7 C.
with an activation energy for the overall thermo-osmotic process
that includes both the dissolution and the transport of water and
methanol in the membrane [21]. The fittings of the data to an
Arrhenius equation give a correlation coefficient equal to 0.98,
and the estimated activation energy is 43.8 kJ/mol. It is note-
worthy that this value is similar to those of the activation energy
reported by Rastogi and Singh [10] (34.3 kJ/mol) for cellophane
membrane, and by Dariel and Kedem [22] (28.0 kJ/mol), Men-
gual et al. [23] (42.6 kJ/mol) for cellulose acetate membranes.
3.2. Thermo-osmotic coefcient
It is interesting to point out that it is not observed any dif-
ference between the two solution levels in the reservoirs. Based
on this experimental finding, it may be assumed that the hydro-
static pressure difference between both sides of the membrane
is negligible. The composition of the water/methanol solutions
was analysed in terms of their densities. The densities of the ini-
tial and final solutions in the reservoirs were measured in each
case. It was found that the variation of the density was lower
than 3 wt.% for the most favourable case. Such small variation
is probably due to the fact that the mass transported across the
membrane is very small compared to the mass of the solutions
in the reservoirs. As the variation of the density is lower that the
accuracy of its experimental determination, it seems reasonable
to consider that the composition of the initial and final solutions
in the reservoirs were the same, within the experimental accu-
racy. Consequently, in the absence of pressure and concentration
differences, the overall flux of a pure solvent i, Ji0 , through the
membrane is given by the following equation [1,2,24]:
Ji0 = Di0
T (2)
where Di0 is the apparent thermo-osmotic coefficient of the sol-
vent. If Ji0 goes from the cold to the hot side, as it is the present
case, it is considered positive and Di0 is negative. Furthermore,
the thermo-osmotic coefficient can be expressed as follows [6]:
Di0 = (s i si )Di (3)
Table 1
Thermo-osmotic coefficients, hydraulic permeability, molar volumes, entropy
difference, and enthalpy of water and methanol
Water Methanol
D0 (106 kg/m2 s K) 0.75 1.5
Lp (1010 kg/m2 s Pa) 2.79 9.44
v (106 m3 /mol) 18.23 38.19
D* (105 kg mol/m2 J s) 1.53 2.47
s s (J/mol K) 0.049 0.061
where s i si is the difference between the partial molar entropy
of solvent i in the external solution and at the membrane, and
Di is given by the following expression:
Lp
Di =
(4)
vi
where Lp is the hydraulic permeability of solvent i in the mem-
brane, and vi is their partial molar volume, which coincides with
the corresponding molar volume of the solvent in the absence
of an electrolyte.
In the case of pure water or methanol, the thermo-osmotic
coefficient Di0 can be estimated by fitting the data, which are
given in Fig. 5, to Eq. (2). The fittings are deemed to be good with
correlation coefficients equal to 0.94 and higher. The obtained
values of Di0 are shown in Table 1. It is found that the thermo-
osmotic coefficient for water is lower than that of methanol.
Based on previous studies [21,25], it may be stated that the
thermo-osmotic coefficient depends mainly on the mobility of
solvent in the membrane, the mean temperature, and the liquid
uptake of the membrane. In principle, due to the constancy of
the mean temperature in the data given in Fig. 5, the coefficient
Di0 turns out to be independent of the temperature difference in
the cell. The higher value obtained for methanol may be due to
its higher mobility in the membrane [26], and the higher liquid
uptake of the membrane [27,28]. This point will be discussed
later when the influence of the methanol percentage was anal-
ysed.
Early studies have shown that the thermo-osmotic coefficient
is strongly dependent on the viscosity of the solvent. For exam-
ple, Tasaka and Futamura [4] showed that the absolute value of
the thermo-osmotic coefficient of charged membranes increased
with the fluidity (reciprocal of the shear viscosity) of the solu-
tion. In this regard, as the viscosity of methanol is lower than
that of water [29], the thermo-osmotic coefficient of methanol
in the Nafion membrane is higher than that of water. Similar
behaviour was also found by Mengual and Garca-Lopez [14]
and by Vink and Chishti [11] using weak charged cellulose
acetate membranes, and Rastogi and Singh [10] with cellophane
membranes, which found a higher thermo-osmotic coefficient
with methanol than with water. In general, the results pub-
lished recently about non-isothermal transport in membranes are
scarce, and the data found in the literature about thermo-osmosis
in Nafion membranes are referred to Nafion 417 membranes and
aqueous solutions [5,6]. Nevertheless, the values obtained for the
thermo-osmotic coefficient in the present study are of the same
order of magnitude that those published elsewhere [3,5,6].
 J.P.G. Villaluenga et al. / Journal of Membrane Science 274 (2006) 116122 121

The values of hydraulic permeability Lp have been estimated

for pure water and methanol by a method described elsewhere
[28]. The values of the partial molar volume have been taken
from Ref. [29]. Then, it is possible to estimate by using Eqs.
(3) and (4) the difference in the partial molar entropy of solvent
122 J.P.G. Villaluenga et al. / Journal of Membrane Science 274 (2006) 116122
Nomenclature
A membrane area (m2 )
Di0 apparent thermo-osmotic coefficient of compo-
nent i pure (kg/m2 s K)
D overall thermo-osmotic coefficient (kg/m2 s K)
Dideal ideal thermo-osmotic coefficient (kg/m2 s K)
Di coefficient defined by Eq. (4)
J overall thermo-osmotic flux (kg/m2 s)
Ji0 thermo-osmotic flux of pure component i
(kg/m2 s)
Lp hydraulic permeability (kg/m2 s Pa)
m mass (kg)
si partial molar entropy of component i in the mem-
brane (J/mol K)
s i partial molar entropy of component i at the exter-
nal solution (J/mol K)
t time (s)
T temperature (K)
Tb bulk temperature (K)
vi partial molar volume of component i (m3 /mol)
xi mole fraction of component i
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