Separation and Purification Technology 166 (2016) 213–221

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Separation and Purification Technology

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

Solubility of binary mixtures of n-heptane with C4 to C6 alcohols in

polymeric membranes
A. Randová ⇑, L. Bartovská, Š. Hovorka
Department of Physical Chemistry, University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic

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

Article history: Sorption gravimetric and volumetric techniques performed at 25 °C and at atmospheric pressure were
Received 4 February 2016 employed to study the preferential and total sorptions from binary liquid mixtures of heptane + alcohols
Received in revised form 20 April 2016 (butan-1-ol, pentan-1-ol, hexan-1-ol) in a polydimethylsiloxane membrane and to study the volumes of
Accepted 20 April 2016
the swollen membrane. The experimental volume of the swollen membrane was compared with that cal-
Available online 22 April 2016
culated under the assumption that interactions between the polymer and liquid mixture were negligible.
The sorption extents of binary liquid mixture butan-1-ol + heptane into three membranes (Nafion, low-
Keywords:
density polyethylene, and polydimethylsiloxane) were compared. Polydimethylsiloxane and low-density
Membrane separations
Polymers
polyethylene sorb preferentially heptane, Nafion prefers butan-1-ol. Because there is an azeotropic point
Equilibrium on the vapour-liquid equilibrium curve of the system heptane + butan-1-ol, the distillation is not suitable
Sorption as a separation technique. Sorption curve, however, exhibits no azeotrope; membrane separation could
Organic liquid be a suitable alternative.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction The response of three different polymer membranes to the

Membrane separation is often used in food and pharmaceutical
industries. Sometimes it is not possible to use distillation methods,
as for instance in case of azeotropic liquid mixtures, and then the
membrane technology may succeed. On contact of a binary solvent
mixture with a polymer, one of the liquid components usually sol-
vates it preferentially. This selective behaviour of polymeric mem-
branes, displaying a preferential sorption for one of the
components in a mixture of liquids, is the basis of separation in
the pervaporation process. The name of this membrane-based pro-
cess is derived from the two basic steps of the process, firstly the
permeation of the mixture through the membrane, then its evapo-
ration into the vapour phase.
The phenomenon of preferential sorption is best understood in
terms of membrane equilibrium. The preferential sorption is con-
veniently expressed by means of the change in molar fraction of
one of the solvent components [1–7].
The solvent ingresses the membrane, occupies the free volume
spaces within the matrix, and due to interactions of the solvent
molecules with the polymer chain segments the volume dilations
of the matrix material occurs.
⇑ Corresponding author.
E-mail address: randovaa@vscht.cz (A. Randová).
liquid mixtures, consisting of two components differing in char-
acter – one non-polar, heptane - linear hydrocarbon - and the
other one polar – linear alcohol, was chosen as the subject of
this study.
Since large amounts of solvents are used in industrial applica-
tions, the minimisation of their environmental impacts calls for
the improvement of current technologies for solvent regeneration
or finding new possibilities in this field. However, the distillation
process, commonly used for the solvents separation, is energy-
consuming, and its effectivity may be limited by the vapour–liquid
equilibrium, especially in cases of azeotropic mixtures. The
membrane separation is one of possible alternatives. The sorption
measurements, subject of this study, appear to be an important
tool for the assessment of membrane selectivity. Three membranes
(polydimethylsiloxane, Nafion, and low-density polyethylene)
were used in this work (Fig. 1).
Polydimethylsiloxane (PDMS) is a soft elastomer that can swell
to several hundred percent in suitable solvent. This elastomer has
some special features which make it an interesting membrane
material for organic extraction: high hydrophobicity, high
permeability, good thermal and mechanical resistance and easy
manufacture of the active layer on asymmetric substrates.
Nafion is ion-exchange material. Its unique ionic properties
result from incorporating perfluorovinyl ether groups terminated
with sulfonate groups onto a tetrafluoroethylene backbone [8,9].

http://dx.doi.org/10.1016/j.seppur.2016.04.034
1383-5866/Ó 2016 Elsevier B.V. All rights reserved.
214 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221

Nomenclature

Symbol Description (unit) Vadd volume of swollen polymer, calculated by Eq. (9)
ag‘ separation factor of vapour-liquid equilibrium (cm3 g1
P )
asb separation factor of liquid in membrane-bulk equilib- Vexp experimental volume of swollen polymer (cm3 g1 P )
rium V volume of swollen polymer (cm3)
qb density of liquid (g cm3) V0 volume of dry polymer (cm3)
qP density of dry polymer (g cm3) VE excess volume of binary liquid mixture (cm3 mol1)
XH preferential sorption (mol g1
P ) VmA molar volume of alcohol (cm3 mol1)
m mass of swollen polymer (g) VmH molar volume of heptane (cm3 mol1)
m0 mass of dry polymer (g) xAb molar fraction of alcohol in bulk liquid
MA molar mass of alcohol (g mol1) xAs molar fraction of alcohol in liquid sorbed into mem-
MH molar mass of heptane (g mol1) brane
n0 the number of moles of the initial solution per 1 g of dry xHb molar fraction of heptane in bulk liquid
membrane (mol g1 P ) xHs molar fraction of heptane in liquid sorbed into mem-
nAs the amount of alcohol sorbed into membrane (mol g1 P ) brane
nHs the amount of heptane sorbed into membrane (mol g1 P ) wter
P weight fraction of polydimethylsiloxane in ternary sys-
ns the total amount of liquid sorbed into membrane tem
(mol g1
P ) wter
H weight fraction of heptane in ternary system
Qm the mass swelling degree (g g1
P ) wter
A weight fraction of alcohol in ternary system
QV the volume swelling degree (cm3 cm3 P )
QVcalc the volume swelling degree, calculated by Eq. (15)
(cm3 cm3
P )

Low-density polyethylene film (LDPE) is non-polar semicrys-
talline polymer (crystallinity 45% [10]). It is a widespread material
used for manufacturing various containers, dispensing bottles,
wash bottles, tubing, plastic bags for computer components, and
various molded laboratory equipment.
The systems membrane + liquid in this work have been studied
through various experimental techniques trying to create a com-
prehensive picture. The total sorption was studied by the gravi-
metric technique, the volume of the swollen membrane was
monitored by the optical method and the interferometer was used
to preferential sorption determination.
The first part deals with three systems in which two compo-
nents, polydimethylsiloxane membrane and heptane, are the same
and the third component is represented by various linear alcohols
(butan-1-ol, pentan-1-ol, or hexan-1-ol). In the second part the
responses of three different membranes (polydimethylsiloxane,
Nafion, and low-density polyethylene) to the binary liquid mixture
heptane + butan-1-ol are compared.
2. Theory
2.1. Swelling degrees
(i) the mass swelling degree, i.e. weight change of the mem-
brane, caused by sorption of the liquid, related to the mass
of the dry polymer:
m  m0
Qm ¼ ð1Þ
m0
(ii) the volume swelling degree, expressing the change in mem-
brane volume, again relatively to membrane volume in the
dry state:
V  V0
QV ¼ ; ð2Þ
V0
where m0 and V0, m and V are the masses and volumes of the dry
and swollen polymer membrane, respectively [11,12].
2.2. Preferential sorption
Different affinities of the liquid mixture components towards
the polymer are responsible for the composition of the liquid mix-
ture sorbed by a polymer being different from the composition of
the bulk liquid mixture surrounding the polymer [13]. The extent
of this difference is expressed by the preferential sorption
[11,14]. As all systems under study have one component – heptane
– in common, they are described in terms of heptane. The relation-
ship for the heptane preferential sorption is primary defined:

Swelling is most easily quantified as weight or volume increase XH ¼ ns ðxsH  xbH Þ ð3Þ
of the material in the form of swelling degrees:
where xsH
is molar fraction of heptane in sorbed liquid and xbH
is
molar fraction of heptane in bulk solution. Because the molar frac-
tions of heptane in sorbed liquid is difficult to measure directly, an
indirect way was used. Based on experimental data for the change
in the bulk solution composition, the preferential sorption can be
also described as:

XH ¼ n0  ðxbH;0  xbH Þ ð4Þ

where n0 is the number of moles of the initial binary solution per

one gram of dry polymer, and xbH;0 is the molar fraction of heptane
in the bulk initial solution. The total amount of binary liquid sorbed
Fig. 1. The structures of membranes: (top) Nafion, (down left) polydimethylsilox- in one gram of a dry polymer (ns) can be expressed from the weight
ane, (down right) low-density polyethylene. uptake
 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221 215

Qm where xi and yi are the molar fractions of the component i in equi-

ns ¼ ð5Þ
Ms librium liquid and vapour phases, respectively).

where Ms (Ms ¼ xsH MH þ ð1  xsH ÞM A ) is the average molar mass of

the sorbed binary liquid, MH and MA are the molar masses of the 2.6. Ternary systems
pure components (H = heptane and A = alcohol: butan-1-ol,
pentan-1-ol, hexan-1-ol). The composition of the liquid sorbed in The composition of swollen polymer (ternary phase) is
the polymer phase may be then obtained as: expressed in weight fractions (the molar mass of the polymer is
not known). The weight fraction of polymer (P) in the ternary sys-
Q m xbH þ XH M A tem (superscript ter) is given by the mass swelling degree as
xsH ¼ ð6Þ
XH ðM A  M H Þ þ Q m
1
P ¼
wter ð12Þ
1 þ Qm
2.3. Individual sorption
and weight fractions of alcohol (A) and heptane (H) are calculated
The sorbed amount of single components is called individual from the composition of the liquid sorbed in the polymer phase:
sorption, nsH (heptane) and nsA (alcohol). It can be calculated by
nsH  MH
combination of the total amount of sorbed liquid (ns) and binary H ¼
wter ð13Þ
1 þ Qm
liquid composition in swollen polymer (xsH and xsA ):
nsA  M A
nsH ¼ xsH  ns ð7Þ wter ¼ ð14Þ
A
1 þ Qm
nsA ¼ xsA n s
ð8Þ
(the base for all the above mentioned quantities is 1 g of dry poly-
mer membrane).
2.4. Volume changes

3. Experimental
In interpreting the thermodynamic properties of real systems it
is customary and convenient to compare them with an ‘‘ideal”
3.1. Gravimetric measurements
behaviour and equations for ideal state. A widespread way how
to find the ideal volume of the swollen membrane is to express it
The total amount of the sorbed liquid has been determined by a
as a sum of the volumes of dry membrane and of the sorbed liquid
gravimetric method [10,11]. A pre-weighed circular disc-shaped
[3,15–18]. Further approximation considers the swollen polymer
sample of the dry polymer membrane was immersed into an
as an ideal mixture of the dry polymer and real binary liquid,
excessive amount (msolution/mpolymer  100) of the respective sol-
expressing its volume as the sum [11]:
vent mixture of an exactly known composition in a tightly sealed
1 flask and allowed to reach sorption equilibrium. The wet mem-
V add ¼ þ ns ðxsH  V mH þ xsA  V mA þ V E Þ; ð9Þ
qP brane sample was then transferred into a weighing bottle lined
with filter paper and arranged in such a position that only its edges
where Vadd is the volume of the swollen membrane and is related to
touched the paper (Fig. 2). The full bottle was weighed after about
1 g of the dry polymer [cm3 g1 P ]; qP the density of dry polymer
1 h, when the paper had drained off the excess liquid from the
[g cm3]; ns the equilibrium mole number of liquid sorbed in 1 g
membrane and the equilibrium in the bottle was established. The
of dry membrane [mol g1 P ], calculated from the weight uptake
foil was then quickly taken out and the bottle with the wet paper
(Eq. (5)); VmH, VmA are molar volumes of pure liquid penetrants:
was weighed again. The difference represented the weight of the
heptane (H) and alcohol A = butan-1-ol, pentan-1-ol, or hexan-1-
swollen foil (m). This procedure was found to be reproducible to
ol [cm3 mol1]; and VE is the excess molar volume of the binary sol-
±2 mg. The results are expressed as the mass swelling degree Qm
vent [19,20]. However, even these volume values, calculated under
(Eq. (1)).
the assumption of the additivity of the dry polymer and real binary
liquid, are often very different from experimentally determined vol-
umes of the swollen membrane. The term additive volume, used in 3.2. Volumetric measurements
this text, has the meaning of an ideal mixture of the dry polymer
and real binary liquid, as described by the Eq. (9). The linear inter- The volume of the swollen membrane, Vexp, was determined
polation between the volume of the pure liquids would comprise from the dimensional changes of the square membrane samples
other two ideal assumption: (i) the excess volume in liquid mixture (1  1 cm). Two dimensions in the plane of the membrane sheet
does not exist, (ii) the mass swelling degree is linear interpolation
between the swelling degrees of the pure liquids.

2.5. Separation factors

The effectiveness of the membrane separation process can be

expressed by the separation factor
xsH =xsA
asb
HA ¼ ð10Þ
xbH =xbA
This quantity can be compared with the relative volatility, a
measure of the relative ease or difficulty of separating the two
components by distillation:
yH =yA
ag‘
HA ¼ ð11Þ Fig. 2. The arrangement of membrane in weighing bottle: (left) the bottle lined
xH =xA with filter paper, (right) the inside of bottle without filter paper.
216 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221
Fig. 3. Dry (left) and swollen (right) polydimethylsiloxane with embroidering.
were monitored directly in liquid by the optical method, which has
been described in our previous papers [11,12].
Because the membrane is hardly visible (or non-visible), the
embroidering was used (Fig. 3). It is four independent thin threads
(cotton yarn into organic liquid, nylon thread into water – this
selection prevents swelling of the threads). This technique permits
easy monitoring of the dimensions of embroidered tetragon.
The third dimension, thickness, was measured immediately
after taking the membrane out of the liquid by an Inductive Dial
Indicator Mahr. The experimental errors in the percentage relative
expansion were determined to be ±2 and ±3 for the optical and
thickness measurements, respectively.
The experimental volume is then calculated from the three
dimensions of membrane sample, and related to one gram of dry
membrane.
3.3. Concentration measurements
To determine the preferential sorption, the change in heptane
concentration in the bulk solution brought about by its contact
with polymer, was measured. Exactly weighed amounts of the
dry polymeric foil cut into small pieces and of the binary liquid
solution with a known composition were kept in a tightly sealed
bottle at constant temperature for 24 h and stirred often. The dif-
ference in heptane content in the initial and equilibrium solutions,
xbH;0  xbH , was then determined using the Rayleigh-Haber-Lowe dif-
ferential interferometer (Carl Zeiss, Germany) with a 0.5-cm dou-
ble cell (maximum difference in the molar fractions ±0.02)
[14,21]. The preferential sorption was calculated from Eq. (4).
3.4. Materials
Polydimethylsiloxane RTV 8335 (Momentive Performance
Materials, USA) is a liquid two-component room temperature vul-
canization silicone rubber, viscosity of base is 70.0 mPa s and vis-
cosity of catalyst is 1100 mPa s, both at 20 °C [22]. The mixed
material will vulcanise at room temperature by an addition reac-
tion. The membrane was prepared as follows: the base (one com-
ponent) was mixed with an excess of pentane and stirred until
the mixture was flowing freely and then the second component
(catalyst) was added. The pentane was the removed in the stream
of air dried by silicagel, the evaporating pentane being collected in
the trap filled with ethanol + dry ice mixture. The rest of mixture
was left to vulcanize in the open air for about 20 h. Its density
(qP = 1.069 ± 0.003 g cm3) was determined by weighing of the
sample of known area and thickness (thickness measured by an
Inductive Dial Indicator, Mahr, Germany). The membrane con-
tained the base and the catalyst in the ratio 10:1. A fresh mem-
brane sample was used for each measurement.
Nafion N-115 [23] (thickness 0.136 mm – measured by an
Inductive Dial Indicator Mahr, density 1.926 ± 0.004 g cm3 –
determined by weighing of the sample of known area and
thickness) was used as received (DuPont). The mass of dry Nafion
membrane at 0% RH was determined in the dry box (glove box with
nitrogen atmosphere containing neither oxygen nor water vapour).
The membrane samples were deposited in this box for 24 h before
weighing (after this period the mass of the membrane remained
constant), and after weighing the membrane sample was trans-
ferred into liquid still in the glove box [24]. A fresh membrane
sample was used for each measurement.
High-pressure low-density polyethylene BRALEN FB 2-30
(LDPE) [25] in the form of foil (thickness 0.046 mm) was used
(Slovnaft, Bratislava). Its density, (q = 0.940 g cm3), was deter-
mined by weighing of the sample of known area and thickness
(measured by an Inductive Dial Indicator, Mahr, Germany). Prior
to experiments, the foil was washed with distilled water, dried in
the drying box for 20 h at 60 °C and then kept in a vacuum desic-
cator. A fresh membrane sample was used for each measurement.
All solvents were p.a. purity grade and were provided by
Sigma-Aldrich, the TRC Tables [26] are used as the source of the
cited density values. All experiments were carried out at 25 °C
and at atmospheric pressure.
4. Results and discussion
4.1. Systems PDMS + pure liquid
The sorption results of systems PDMS + pure liquids are pre-
sented in Table 1. PDMS swells markedly in the presence of hep-
tane (Qm = 3.08, QV = 6.32), but only slightly in the presence of
alcohols (Qm = 0.11 – 0.14, QV = 0.16 – 0.18). Both swelling degrees
as well as the swollen membrane volumes in all three alcohols are
nearly the same and moreover there is practically no difference
between the Vexp and Vadd within the experimental errors. It can
be said that to assume the additivity of volumes (Eq. (9)) is not
erroneous in this case.
A slight trend can be detected only in mass swelling degree in
systems PDMS + alcohol (the higher alcohol the lower value).
The volume swelling degree of PDMS in heptane is noticeably
higher than the mass swelling degree, and the experimental and
calculated volumes are different. In this case the assumption of
additivity is out of place. It can be observed that the presence of
OH-groups does not support the swelling process of PDMS, but
the presence of heptane (it means only hydrocarbon chain) sup-
ports the swelling. Because the alcohol is sorbed firstly into the free
volume and on the membrane surface, it can be said that the pres-
ence of alcohol has small influence on the arrangement of mem-
brane chains, due to the differences in structures of alcohol and
membrane. On the other side, the heptane is massively sorbed
between the polymer chains, and causes moving the polymer
chains apart.
Some literature data for the system PDMS + butan-1-ol were
found, but at higher temperature and at different condition – for
example, the membrane is from another manufacturer, or the ratio
base: catalyst (B:C) is different from our or not known. Various
quantities specified in these articles were converted into swelling
degree (Qm). The results are compared in Table 2. Our results
closely correspond with those of other authors.
Table 1
Sorption data of PDMS in pure liquids.
Liquid Qm Vadd Vexp QV
Heptane 3.0812 5.47 6.84 6.32
Butan-1-ol 0.1390 1.11 1.08 0.15
Pentan-1-ol 0.1216 1.09 1.09 0.16
Hexan-1-ol 0.1076 1.07 1.11 0.18
 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221
Table 2
Sorption data of PDMS in butan-1-ol.
This work [27] [28] [29]
Qm 0.139 0.191 0.187 0.287 0.283
t (°C) 25 40 40 40 42
B:C 10:1 – 5:1 20:1 – –
4.2. System PDMS + binary liquid mixture
4.2.1. Preferential sorption and sorption diagram
The experimental data on the concentration changes of the bulk
solution, which were caused by the sorption of binary liquid mix-
tures in PDMS, were plotted as composite isotherms, i.e., the pref-
erential sorption vs. the equilibrium bulk solution composition. It
is always heptane which is preferentially sorbed in PDMS over
the alcohol. The composite isotherms (Fig. 4A) are of the common
n-shape. The highest value of heptane preferential sorption
(XH = 25  104 mol g1 P ) is observed in system PDMS + butan-1-
ol + heptane. The height of the maximum on the composite iso-
therm decreases with increasing number of carbon atoms in alco-
hol. To illustrate the composition changes of the binary liquid
mixture on its entering into the polymer, a diagram showing the
relationship between the molar fractions of heptane in the sorbed
liquid mixture, xsH , and those in the bulk solution surrounding the
polymer, xbH , is shown in Fig. 4B.
It demonstrates that the polydimethylsiloxane membrane is not
too suitable for separation of these mixtures and that the differ-
ences between butan-1-ol, pentan-1-ol, and hexan-1-ol are small.
exp
4.2.2. Comparison of experimental (V ) and calculated (V )
volumes of the swollen membrane
The curves of experimental volumes are S-shaped and flatten
out with increasing number of C-atoms in alcohol.
In all three systems there are differences between the experi-
mental and calculated volumes of swollen membrane, especially
at high heptane contents (Fig. 5). The highest discrepancies are
observed in the system with the lowest alcohol, PDMS + butan-1-
ol + heptane. The length of hydrocarbon part is the smallest in
butan-1-ol (so this alcohol has the most ‘‘alcoholic character‘‘).
The ‘‘alcoholic character‘‘ in hexan-1-ol is less apparent, therefore
the non-ideality is not so big.
4.2.3. Swelling degrees
Fig. 4 shows equilibrium mass and volume swelling degrees in
the dependence on the binary bulk liquid composition. The volume
Fig. 4. Composite isotherms (A) and sorption diagram (B).
217
swelling degree (QV) is always higher than the mass one (Qm). This
difference is negligible at small alcohol contents, but it increases
[30] with increasing heptane concentration, i.e. with decreasing polar-
0.1746 ity of the bulk solution. It can be seen that simple calculation of
40 volume swelling degree from the polymer weight increase,
qP
Q calc ¼ Qm  ð15Þ
V
qb
where qP and qb are the densities of dry polymer and bulk binary
liquid, is not adequate. The calculated QVcalc are denoted by full lines
(Fig. 6).
4.2.4. Individual isotherms and ternary diagrams
The individual isotherms of systems PDMS + heptane + butan-
1-ol, PDMS + heptane + pentan-1-ol, PDMS + heptane + hexan-1-
ol, calculated by Eqs. (7) and (8), together with total amount of
sorbed liquid (ns), calculated by Eq. (5), are shown in Fig. 7.
Although the amount of sorbed heptane is significantly higher than
the amount of sorbed alcohol, the difference between total amount
and heptane amount in all three systems is evident, therefore the
separation is not too good.
The ternary phase diagram is presented in Fig. 8. The composi-
tions of both equilibrium phases, of the swollen polymer (empty
symbols) and binary bulk solution surrounding the polymer (full
symbols) are connected by tie-lines (thin full lines). The lowest
value of weight polymer fraction is observed in system PDMS
+ pure heptane (wter P = 0.245), the highest ratio of polymer fraction
to liquid fraction is in system PDMS + pure hexan-1-ol
 ter 
wP
¼ 9:3 . It corresponds with lowest value of sorption of
wter þwter
H A
hexan-1-ol into PDMS, presented in Table 1.
add
4.2.5. Separation factors
The distribution of heptane/alcohol mixture in and out PDMS
membrane are presented in Fig. 9 in the form of separation factors.
The figure shows that the differences between alcohols are very
small.
4.3. Comparison of PDMS, LDPE, and Nafion behaviour in mixtures
butan-1-ol + heptane
The first membrane, PDMS, is hydrophobic and in presence of
alkanes and aromatic compounds swells considerably, but the
swelling degree in alcoholic medium is very small (Fig. 10). Nafion
has opposite properties. It is hydrophilic and its swelling in alkanes
is close to zero; on the other hand this membrane swells in pres-
ence of alcohols. It is supposable that both of these membranes
218 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221

Fig. 5. The experimental and calculated volumes as a function of molar fraction of heptane in equilibrium bulk solution: (A) PDMS + butan-1-ol + heptane, (B) PDMS
+ pentan-1-ol + heptane, (C) PDMS + hexan-1-ol + heptane.

Fig. 6. Mass and volume swelling degrees as a function of molar fraction of heptane in equilibrium bulk solution – comparison of the systems: PDMS + heptane + C4, C5, and
C6 alcohols.

Fig. 7. Individual isotherms of systems (A) PDMS + heptane + butan-1-ol, (B) PDMS + heptane + pentan-1-ol, (C) PDMS + heptane + hexan-1-ol.

Fig. 8. Ternary diagrams of systems (A) PDMS + heptane + butan-1-ol, (B) PDMS + heptane + pentan-1-ol, (C) PDMS + heptane + hexan-1-ol.

can be used to separation of mixture butan-1-ol + heptane. But it is including both, preferential and total sorption. Because there is an
not true. Although the maximal absolute values of preferential azeotropic point on the VLE-curve [31] of the system heptane
sorption are of the same order (XH (PDMS) = 25  104 mol g1 P + butan-1-ol, the distillation is not too suitable as a separation
and XH (Nafion) = 32  104 mol g1 P ), the sorption diagrams are technique. As can be seen from Fig. 11 (right), contrary to VLE-
widely different (Fig. 11). The highest values of preferential sorp- curve, there is no azeotrope on the sorption curves. The inspection
tion of heptane in systems with LDPE is lower (XH (LDPE) of the sorption diagram yields the following conclusions: only the
= 4.5  104 mol g1
P ). The sorption diagram is complex information membrane separation using Nafion is very promising.
 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221
Fig. 9. Separation factors of systems PDMS + heptane + alcohol: black points = bu-
tan-1-ol, grey points = pentan-1-ol, empty points = hexan-1-ol.
The individual sorptions of system with PDMS reach the biggest
values, but the difference between heptane and alcohol is not sig-
nificant. The individual isotherm of butan-1-ol in Nafion is very
near to the curve of the total sorption; therefore the total amount
of the sorbed liquid consists mainly of butan-1-ol, it means that the
mixture heptane + butan-1-ol could be well separated. The sorbed
amounts of the individual components in the system LDPE +
heptane + butan-1-ol are very small (see Fig. 12).
The ternary phase diagram is presented in Fig. 13. The compo-
sitions of both equilibrium phases, of the swollen polymer and
binary bulk solution surrounding the polymer are connected by
tie-lines (thin full lines). This figure comprises two pieces of
information – (i) the ability of membrane to sorb certain mass of
liquid, (ii) and which of the liquid mixture components is sorbed
preferentially. It can be seen that the extent of the liquid sorption
into LDPE is small, nevertheless the experimental data indicate
that the mass of sorbed heptane is higher than the mass of
butan-1-ol. PDMS noticeably sorbs both, heptane and butan-1-ol.
The total sorption of this liquid mixture into Nafion is lower than
its sorption into PDMS, but the preference of this membrane for
the mixture components is reversed: the sorption of butan-1-ol
significantly exceeds sorption of heptane.
The appraisal of the possibility to use the membrane for the
separation processes can be adequately expressed in terms of
Fig. 10. Mass (A) and volume (B) swelling degrees as a function of molar fraction of heptane in equilibrium bulk solution – comparison of Nafion, LDPE, and PDMS.
219
separation factors. It is difficult to summarize the separation fac-
tors for all three systems (PDMS + heptane + butan-1-ol, Nafion
+ heptane + butan-1-ol, LDPE + heptane + butan-1-ol) into one fig-
ure, because the sorption separation factor is defined always for
the preferentially sorbed component. The separation factors are
separated into two graphs – one for LDPE and PDMS (Fig. 14A, hep-
tane is preferentially sorbed) and second for Nafion (Fig. 14B,
butan-1-ol is preferentially sorbed). For the sake of illustration
the distillation separation factor was plotted into both graphs, as
ag‘
HA in Fig. 14A, and as aAH in Fig. 14B. The system with Nafion exhi-
g‘
bits the highest absolute values of separation factors. These data
indicate that the separation of mixture heptane + butan-1-ol
would be most successful using Nafion membrane.
5. Conclusions
5.1. The influence of alcohol on the behaviour of PDMS in liquid
mixtures n-heptane + C4, C5, and C6 alcohols
The results of the weight uptake measurements for the poly-
dimethylsiloxane membrane (thickness of 1 mm) on its immersion
into three binary liquid mixtures of heptane with alcohols (butan-
1-ol, pentan-1-ol, and hexan-1-ol) in the whole concentration
range are presented at the temperature of 25 °C and atmospheric
pressure.
The mass swelling degree values in pure alcohols are low (the
lowest value is Qm = 0.11 in hexan-1-ol), contrary to value in pure
heptane (Qm = 3.08). This corresponds to the observed fact that the
preferential sorption of heptane is higher than the preferential
sorption of any of alcohol. The height of the maximum on the pref-
erential sorption curve decreases from system with butan-1-ol to
system with hexan-1-ol.
The dimensional response data have shown that the membrane
volume changes in system PDMS + heptane are caused not only by
entering a certain amount of liquid into the membrane but also by
interactions between the polymer and the solvent. Real mixtures
do not behave ideally, therefore it is forced to introduce a correc-
tion terms to values quantities determined on the basis of pure
substances (one pure substance is dry polymer, second pure sub-
stance is liquid mixture). This non-ideality can be imagined as
some kind of interaction – it means that the presence of heptane
causes moving away of the polymer chains, whereas in the pres-
ence of alcohol the distance between the polymer chains is
retained (to some extent). How can be deduced from the fact that
the difference between the experimental and calculated volumes is
220 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221

Fig. 11. Suitability for membrane separation – preferential sorption (A) and sorption diagram (B) – comparison of Nafion, LDPE, and PDMS.

Fig. 12. Individual isotherms of systems (A) PDMS + heptane + butan-1-ol, (B) Nafion + heptane + butan-1-ol, (C) LDPE + heptane + butan-1-ol.

Fig. 13. Ternary diagram of systems d PDMS + heptane + butan-1-ol, j Nafion + heptane + butan-1-ol, r LDPE + heptane + butan-1-ol.

Fig. 14. Separation factors of systems (A) d PDMS + heptane + butan-1-ol, } LDPE + heptane + butan-1-ol, (B) h Nafion + heptane + butan-1-ol, comparison with  VLE.
 A. Randová et al. / Separation and Purification Technology 166 (2016) 213–221
nearly the same for all three binary systems PDMS + butan-1-ol,
+ pentan-1-ol, + hexan-1-ol, the influence of all three alcohols on
PDMS swelling is very much alike.
The sorption diagram and individual isotherms show that the
separation of PDMS is not great, therefore other membranes were
tested.
5.2. Comparison of the behaviour of different membranes in the butan-
1-ol + heptane mixture
On the basis of experimental sorption data the three mem-
branes, PDMS, LDPE, and Nafion, were compared with respect to
their ability to separate liquid mixture butan-1-ol + heptane. PDMS
and LDPE sorb preferentially heptane, Nafion shows greater affinity
to butan-1-ol. In case of PDMS the preferential sorption has rela-
tively high values, but considering high values of total sorptions,
the resulting separative effect is negligible. The separation ability
of LDPE seems to be reasonable, but the total sorption values are
too low for its practical application. Contrary to vapour-liquid
equilibrium none of the sorption curves exhibits an azeotrope.
Generally, all three membranes respond to the presence of the
chosen liquids, but only two of them (Nafion, LDPE) show separa-
tion ability. It can be concluded that the most effective separation
can be achieved using Nafion.
Acknowledgement
Authors thank to UCT Prague Institutional support.
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