Journal of Membrane Science 150 (1998) 125141

Comparison of UNIQUAC with related models for

modelling vapour sorption in polar materials
Anne Jonquieres*, Laurent Perrin, Stephanie Arnold, Pierre Lochon
Laboratoire de Chimie-Physique Macromoleculaire, CNRS UMR 7568, ENSIC, 1 rue Grandville, BP 451, 54 001 Nancy Cedex, France

Received 4 May 1998; accepted 14 July 1998

Abstract

By a systematic investigation of solvent polymer systems of even greater complexity, this work analyses the relative
performances of UNIQUAC and related models to account for sorption phenomena in polar elastomers (polyurethaneimides)
with vapours of moderate to strong polarity (ether, ester, alcohol).
Four different UNIQUAC-type models have been chosen for this study: UNIQUAC, UNIQUAC-HB, UNIQUAC-FV and
UNIQUAC-FVHB. They mainly differ in corrective and/or additional terms accounting for particular effects such as free
volume (FV) effects or hydrogen bonding (HB) or a combination of both (FVHB). Their main respective advantages are
discussed with regard to the solvent and polymer chemical structures and the type of interactions involved in the sorption
phenomenon.
UNIQUAC-FV is shown to provide the best results for the sorption of aprotic species (ether, ester) in polyurethaneimides, as
could be expected for elastomers for which free volume effects are usually believed to be signicant. However, the sorption of
a protic species (alcohol) is best described by UNIQUAC-HB, i.e. the UNIQUAC model specically modied for systems
involving strong interactions by hydrogen bonding. Hydrogen bonding could therefore prevail on free volume effects for these
particular systems. # 1998 Elsevier Science B.V. All rights reserved.

Keywords: Polyurethaneimides; Sorption; UNIQUAC; FloryHuggins

1. Introduction drastic inuence of water vapour sorption on mechan-

A wide range of industrial processes and applica-
tions involve polymer materials in contact with
vapours or liquids. In all these cases, polymer materi-
als usually absorb a given amount of vapour or liquid
and this swelling behaviour can inuence the process
design and/or the material performances very signi-
cantly. Very common examples are related to the
*Corresponding author. Tel.: +33-3-83-17-50-29; fax: +33-3-83-
37-99-77.
ical (epoxide resins) or electrical (polyimides) mate-
rial properties. Polymer purication processes as well
as membrane based separation systems can also be
governed to a great extent by sorption phenomena in
polymeric materials. Therefore, a basic knowledge of
the swelling behaviour of polymeric materials is
required for a proper design and optimisation.
Several approaches have been reported for describ-
ing the sorption phenomenon in polymer materials.
One of the most used approaches is due to Flory [1]
and Huggins [2] who derived a rather simple model

0376-7388/98/$ see front matter # 1998 Elsevier Science B.V. All rights reserved.
PII: S0376-7388(98)00221-X
126 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141
based on a basic lattice concept. In the frame of this
theory, the modelling of polymer behaviour during
vapour sorption can be achieved by using a single
parameter known as the FloryHuggins parameter.
Despite its theoretical restriction to apolar species
[3] this theory has been applied to a wide range of
systems [3] and the initial theory has also been lately
rened to account for sorption in systems of ever
increasing complexity [47].
Another interesting approach is the dual sorption
theory which was derived initially for glassy materials
[8]. In addition to providing a new description for
sorption isotherms in complex media, the dual sorp-
tion theory allowed new interesting insights into the
diffusion phenomena in polymeric materials [8].
Related theories have recently somewhat overcome
the difculties encountered with polymers inducing
high swelling ratio for which the initial dual sorption
theory was proved to be inaccurate. Interesting results
could then be obtained even for systems strongly
deviating from ideality [9].
Quite recently, a purely mechanistic approach was
shown to be a very good alternative to the former
models. This approach considers the sorption phe-
nomenon as a competitive process of sorption on two
different sites, i.e. a polymeric site or another pre-
viously sorbed molecule. This model (referred to as
the ENgaged Species Induced Clustering model
(ENSIC)) enabled the sorption modelling for a very
broad range of systems [10,11], even including
adsorption on mineral sorbents [12].
During the last few years, a great deal of work on
polymer solvent systems has also been achieved by
many scientists in chemical engineering. Their main
purpose was the use and extension of well-known
chemical engineering models which has been initially
established for liquidvapour equilibrium (LVE) cal-
culations. Amongst these were the UNIQUAC model
and other related approaches which can, at least
theoretically, allow the modelling of very complex
systems providing that the behaviour of the derived
binary systems be known. In other words, only second
order (i.e. binary) parameters are theoretically
required whatever the order of the systems investi-
gated. In this paper, the literature background devoted
to UNIQUAC and related calculations of the thermo-
dynamics of binary polymer solvent systems are
briey reviewed. Four UNIQUAC-type models are
then assessed for accounting for polymer swelling
in systems involving moderate to strong interactions.
2. Literature background
In this part, the main contributions to sorption
modelling in binary solvent polymer systems by
UNIQUAC and related models are briey reviewed.
The different types of binary systems and models
investigated are focused on in detriment of the details
of the different models which are the scope of the
following section.
In 1975, Abrams and Prausnitz reported a new
approach, the UNIversal-QUAsi Chemical
(UNIQUAC) model, which was shown to be applic-
able even to mixtures including a polymer phase. In
this pioneering paper, the vapour sorption of two
solvent polymer systems (i.e. benzene/polyisobuty-
lene; water/polyethyleneglycol) could be well
accounted for by the UNIQUAC equation [13].
A few years later, Oishi and Prausnitz extended to
polymer solutions the group contribution method
UNIFAC which is a fully predictive method very
closely related to UNIQUAC. This model takes into
account free volume (FV) effects which can be of high
importance for polymer systems and is thus usually
referred to as UNIFAC-FV. Thirteen binary solvent
polymer systems were chosen for this rst investiga-
tion. The UNIFAC-FV model allowed a fairly good
prediction of solvent activities with errors of about
10% [14].
Most likely driven by potential applications and a
strong industrial interest, a lot of contributions have
been reported during the last ten years. The sharp
increase in the number of papers during the last few
years proves a strong scientic activity in this eld
with a major contribution of scientists in membrane
science and technology. Table 1 summarises the main
contributions for binary systems, thus involving sorp-
tion of pure vapours in polymer materials. A few
references on systems of higher orders (such as ternary
or quaternary systems) have also been reported in
Table 1 only when they involve a specic study of
the related binary systems as a preliminary require-
ment for the modelling of the more complex systems.
From Table 1, most of the studies involve the use of
a single UNIQUAC-type model, the most common
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141 127

Table 1
Binary solvent polymer systems: modelling by UNIQUAC and related models

Reference Model Polymer/solvent systems

[13] UNIQUAC Polyisobutylene (PIB)/benzene; PEG/water

[14] UNIQUAC-FV Thirteen systems, mainly systems of low polarity
UNIFAC-FV Polymers: PIB, PEG, PVAc, PS; solvents: aromatics, alkanes, ester, ketone
[15] UNIFAC-FV, method of IlyasDoherty, Sorption of 35 solvents in natural rubber including highly polar species such
method of HoltenAndersen as acids and alcohols

[16] UNIQUAC Polymer: polyurethane (PU), solvents: benzene, cyclohexane

[17] UNIQUAC Polymer: PU, polyether-block-amide (PEBA), solvents: benzene, cyclohex-
ane, cyclohexene
[18] UNIQUAC Polymer: PU, solvents: benzene, toluene, cyclohexane
[19] UNIQUAC-HB Polymer: PVA, solvents: water, alcohols, acetone, dioxane, THF
[20] UNIQUAC-FV Polymer: PVAc, solvents: MeOH, EtOH, benzene
[21] UNIFAC-M-H Polymers: PE, PP
UNIFAC-F-R Solvents: alkanes (n-butane->n-heptane)
[22] UNIQUAC Polymers: PU, PEBA, solvents: benzene/cyclohexene/cyclohexane
[23] Modified NRTL model Ten systems including systems involving strong interactions
[24] UNIFAC, UNIFAC-FV, UNIFAC-r Fifty one systems including a few species of high polarity
[25] UNIFAC-FV Polymer: Polymethylacrylate (PMA), solvents: chloroform, CCl4, benzene,
toluene, n-hexane

one being UNIFAC-FV. A few references focus on the
comparison between UNIFAC-FV and other
approaches such as UNIQUAC [14,24] or other more
recent related models which bring new interesting
ways of improving the initial UNIQUAC model
[15,21,24]. However, systematic comparative studies
between different UNIQUAC-type models are rela-
tively scarce for solvent polymer systems.
Also worthy of mention, the great majority of
solvent polymer systems investigated up to now
involves species of low to moderate polarities which
usually do not display specic interaction of strong
intensity. Therefore, the very particular case of sys-
tems involving strong specic interactions (e.g. hydro-
gen bonding, etc.) remains of great interest. They
usually lead to systems deviating strongly from ide-
ality which are particularly good systems to assess the
reliability of thermodynamic modelling models.
Examples of such systems are mostly found in recent
studies such as those reported by Heintz and Stephan
[19], Saure and Schlunder [20] and Wu et al. [23].
Typical highly non-ideal systems involve protic sol-
vents (e.g. alcohols and water) and mildly to strongly
polar polymers (e.g. polyethyleneglycol, polypropyl-
eneglycol, polyvinylalcohol, polyvinylacetate, etc.).
For these systems involving specic interactions by
hydrogen bonding, the UNIQUAC-HB model derived
by Abrams and Prausnitz [13] has been found to be an
interesting approach as typically shown by Heintz and
Stephan [19].
3. Theory
In this paper, we want to assess in a systematic way
four different UNIQUAC-type models for systems of
moderate to strong polarity including systems invol-
ving strong specic interactions. These models are:
(i) UNIQUAC
(ii) UNIQUAC-HB
(iii) UNIQUAC-FV
(iv) UNIQUAC-FVHB.
As shown in Table 2, these models are based on the
same general theoretical ground and they mainly differ
in corrective or additional terms taking into account
particular effects related to polymeric materials (free
volume) or specic interactions (hydrogen bonding).
3.1. The UNIQUAC model
UNIQUAC is the rst model to be considered
because it is the initial approach [13]. It has been
shown to be relevant to a wide range of binary solvent
polymer systems as described in a former part of the
128 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141

Table 2
The different UNIQUAC models investigated

Model Comments ln ai

UNIQUAC [13] UNIversal QUAsi Chemical ln aCi ln aRi

UNIQUAC-HB [26] Influence of hydrogen bonding ln aCi ln aiRHB
UNIQUAC-FV [14] Influence of free volume (polymer systems) ln aCi ln aRi ln aFV
i
UNIQUAC-FVHB Combined influence of free volume and hydrogen bonding ln aCi ln aiRHB ln aFV
i

paper. Since it provides the common theoretical basis of the UNIQUAC model, the binary interaction
for the other models investigated, it should also give parameters are considered as adjustable parameters
reference results for this comparative case study. (contrary to the derived approach UNIFAC which, at
The UNIQUAC model provides a description of the least theoretically, allows a full prediction of the
activity of component i (ai) as the sum of a combi- thermodynamic behaviour). For the systems investi-
natorial part (aCi ) mainly due to differences in size and gated in this work, only UNIQUAC could be used,
shape and a residual part aRi reecting energetic most of the increments which would be required for
interactions [13,27]: the polymer component being missing in the UNIFAC
increment tables. Therefore, the binary interaction
ln ai ln aCi ln aRi : (1) parameters had to be calculated by a non-linear
For a binary system involving a solvent (component 1) regression technique as further described in the experi-
and a polymer (component 2): mental part.
 
C z 1 r1
ln a1 ln 1 q1 ln 2 l1 l2 ; (2) 3.2. The UNIQUAC-HB model
2 1 r2
ln aR1 q1 ln 1 2 21 UNIQUAC-HB is usually considered as more accu-
  rate for systems involving strong specic interactions
21 12
2 q1 ; (3) by hydrogen bonding [26,29]. It will be assessed for
1 2 21 1 12 2
the systems involving a protic species (ethanol) and
z
li ri qi ri 1; (4) polymer materials containing Lewis basic sites which
2 were previously shown to involve strong H-bonds with
with i and i being the volume fraction and the protic compounds [30,31].
surface fraction of component i, respectively. The The UNIQUAC-HB model accounts for hydrogen
calculation of i and i requires the UNIQUAC para- bonding by a new residual part (aRi -HB ), the combi-
meters ri and qi for the pure components. These can be natorial part remaining unchanged, as could be
found in reference tables or calculated from the mole- expected since hydrogen bonding mainly affects the
cular structures by group-contribution methods energetic interactions:
[27,28].
ln a ln aC ln aR-HB :
i i i (7)
ri x i
 i Pn ; (5) For the solvent (component 1), it follows:
j1 rj xj
qi x i ln a1R-HB q01 ln 01 02 21
 i Pn : (6)  
j1 qj xj 21 12
02 q01 0 ; (8)
1 02 21 01 12 02
In this development, z is the coordination number
and is usually taken equal to 10.0 [13,27,28]. q0i is a modied surface parameter related to pure
 12 and  21 are the binary interaction parameters component i. It is equal to the UNIQUAC surface
and can be related theoretically to the interaction parameter qi for aprotic species whereas it is inferior to
energy between components 1 and 2. In the frame qi for protic compounds to account for the system
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141 129

contraction expected for molecules displaying strong [14,15,20,21,25]. The parameter b is a proportionality
specic interaction [26,29]. factor and it has been shown b1.28 gives the best
In the same way, 0i is a modied volume fraction results for a wide range of solvent polymer systems
calculated on the basis of the modied surface para- [14]. Despite the former values could be debated or
meter q0i according to taken as adjustable parameters, they were taken as
constants in our numerical calculations for the sake of
q0 x i
0i Pn i 0 : (9) simplicity.
j1 qj xj

3.4. The UNIQUAC-FVHB model

3.3. The UNIQUAC-FV model
Specically dened by Oishi and Prausnitz [14] for
solvent polymer systems, this UNIQUAC-type model
accounts for free volume effects which can be
neglected for small molecules but can be of great
importance for systems involving macromolecules.
The UNIQUAC-FV model provides a new descrip-
tion of solvent polymer systems on the basis of an
additional term for the solvent activity compared to
the initial UNIQUAC approach:
ln ai ln aCi ln aRi ln aFV
i :
Based on a previous theory developed by Flory,
Oishi and Prausnitz proposed the following relation-
ship for the free volume contribution:
Nine solvent polymer systems were chosen for this
case study. All of them involve elastomers for which
free volume effects are believed to be signicant. A
few systems were also previously shown to involve
strong specic interactions by hydrogen bonding
[30,31]. Therefore, a better model to be considered
should theoretically account for both of these effects,
i.e. free volume and hydrogen bonding. The
UNIQUAC-FVHB model combines the additional
and corrective terms of UNIQUAC-FV and
UNIQUAC-HB to provide a unied approach of sorp-
(10)
tion in solvent polymer systems involving strong
interactions,
ln a ln aC ln aR-HB ln aFV ;
i (14)
i i i

2  1=3 3 with the former expressions for the different terms.

hvi1 1
ln aFV 4 5
1 3 c1 ln 1=3
hviMIX 1
4. Materials and procedures
  !1
hvi1 1
c1 1 1 1=3 ; (11) 4.1. Materials and sorption isotherms
hviMIX hvi 1

with The solvents, materials and sorption isotherms

obtained at 308C have already been reported else-
1 where [32]. Typically, the materials are polyuretha-
hvi1 : (12)
15:17 b r1 =M1 1 neimide block copolymers. These polymers associate
For sake of simplicity [14], the reduced volume the same pyromellitimide hard block with soft blocks
related to the solvent polymer mixture hviMIX can be of different chemical natures (polyether -PEG, PPG-,
calculated considering the volume additivity rule by polyester -PCL-). The solvents are of moderate to
strong polarity (ether, ester and alcohol).
w1 =1 w2 =2
hviMIX ; (13)
15:17 b r1 w1 =M1 r2 w2 =M2
4.2. Pure component physico-chemical parameters
i and Mi being the density and the molecular weight
of component i, respectively. 4.2.1. Pure component densities
In this development, 3 c1 is the number of external The solvent and polymer pure component densities
degrees of freedom per solvent molecule. The para- i are required for the sorption modelling by
meter c1 is usually considered equal to 1.1 UNIQUAC-FV.
130 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141

Table 3
Physico-chemical parameters for solvent and polymer pure components

ETBE EtOH AcOEt PUI1 PUI2 PUI3

 (g/ml) (308C) 0.739 0.783 0.888 1.187 1.205 1.174

M (g/mol) 102 46 88 1355 1880 1280
r 4.742 2.106 3.479 49.789 70.108 49.508
q 4.172 1.972 3.116 38.145 55.874 38.496
q0 4.172 0.920 3.116 38.145 55.874 38.496
PUI1: PPG725-MDI-AP; PUI2: PCL1250-MDI-AP; PUI3: PTMG650-MDI-AP. For the different sources, see main text.

The density of ethyl-tert-butyl-ether (ETBE) at international mathematics and statistics library

308C has been calculated from a correlation provided (IMSL), this code calculates the values of the binary
by the Institut Franc,ais du Petrole (ETBE0.739 g/ interaction parameters  12 and  21 which minimise the
ml). The ethanol density calculated from a similar tting error between the experimental and calculated
correlation (EtOH0.783 g/ml) is in very good agree- activity values.
ment with the value reported in the reference book by Also provided is the residual sum of squares of
Riddick and Bunger [33] (0.781 g/ml). The density errors (RSSE) which is usually considered as one of
of ethyl acetate has been calculated from Riddick and the best statistical estimates for non-linear regression
Bunger [33] (AcOEt0.888 g/ml). analysis [34]:
The polymer densities have been measured using a N  2
X
Micromeritics Accu Pyc 1330 pycnometer (accuracy: RSSE yexp ycalc : (15)
j j
1 mg/ml) (Table 3). j1

4.2.2. Pure component UNIQUAC parameters The mean relative error (MRE) has also been
The solvent parameters r, q and q0 were previously calculated because it is a widely used criterion which
reported for ethanol [28,29] and ethyl acetate [28]. is a normalised estimate thus not reecting the vari-
They were calculated from a group-contribution able absolute values:
 
method [27] for ETBE. N ABS y
exp
y calc
100 X j j
The polymer parameters r and q were calculated MRE : (16)
from the molecular structure of the polymer repeating N j1 yexp
j
unit using a group-contribution method [27]. The
polyurethaneimides investigated have been shown to
be very good hydrogen bonding acceptors [30,31]. 5. Results
According to a wide range of previous results, their
potentiality of HB donor is very low and was neglected The results are reported in the order of the systems
for this work, thus implying q0 q, as a similar of ever increasing complexity, the most complex
approach reported for a related material (i.e. polyur- systems involving the strongest interactions between
ethane [1618,22]). the penetrant and the polymer material.
The values for the different pure component para-
meters are reported in Table 3. 5.1. Sorption of ethyl-tert-butyl ether (ETBE)
(Table 4)
4.3. Numerical procedure
ETBE is an aprotic compound of moderate polarity
The experimental sorption isotherms were tted thus involving only mild interactions with poly-
using a Digital VISUAL FORTRAN code for non- urethaneimides.
linear multiparameter regression. Based on a non- The sorption of ETBE leads to rather different
linear double precision regression subroutine of the isotherms depending on the PUI chemical type (e.g.
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141 131

Fig. 1. Sorption of ethyl-tert-butyl ether in polyurethaneimides at 308C. Organic vapour activity vs. weight fraction of solvent in the swollen
membrane. *: experimental data. Modelling curves calculated by UNIQUAC (a)(c) or UNIQUAC-FV (d)(f).

polyetherurethaneimide, polyesterurethaneimide,
etc.) as shown in Fig. 1. The system ETBE/
PPG725-MDI-AP provides a sorption isotherm
(Fig. 1(a)) which could be very well accounted for
by two straight lines with a greater penetrant afnity
towards the polymer material for the highest activities
(typically a>0.5). A very different pattern is found for
the other systems with convex isotherms over the
entire activity range (Fig. 1(b) and (c)). Worthy of
mention are also the extremely low sorption levels
observed for the system ETBE/PCL1250-MDI-AP in
the low activity range (a<0.25). For this system, fair
sorption levels are only reached for activities higher
than 0.5. A closely related trend can be also observed
for the sorption of another solvent chosen for this case
study as will be discussed in a following section (i.e.
ethanol). Both of these penetrants show only a mod-
erate afnity towards the PCL1250-MDI-AP with
maximum values for the penetrant weight fraction
of less than 0.2 and very sharp patterns in the low
activity range.
Since ETBE is an aprotic compound, UNIQUAC
and UNIQUAC-FV were the only models tested for
this particular solvent (Table 4).
132 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141
Table 4
Modelling of the sorption of ethyl-tert-butyl-ether in polyurethaneimides at 308C by UNIQUAC and UNIQUAC-FV
Sorption of ETBE at 308C
 12
PPG725-MDI-AP UNIQUAC 1.710
UNIQUAC-FV 1.965
PCL1250-MDI-AP UNIQUAC 2.074
UNIQUAC-FV 2.389
PTMG650-MDI-AP UNIQUAC 0.955
UNIQUAC-FV 0.247
 12 and  21 are the binary interaction parameters. RSSEresidual sum of squares of errors. MREmean relative error.
As could be expected from the singular shape of the
sorption isotherm for the system ETBE/PPG725-
MDI-AP, the UNIQUAC model can only provide a
good approximation for the isotherm with a mean
relative error of 17.5% (Fig. 1(a)). Though speci-
cally derived for polymer systems, the UNIQUAC-FV
does not provide any signicant improvement com-
pared to the initial UNIQUAC approach (Fig. 1(d)).
The sorption of ETBE in PCL1250-MDI-AP can
fairly well be accounted for by UNIQUAC over almost
all the activity range (a<0.8). However a signicant
modelling error is obtained for the highest activities
with a sharp down-turn of the modelling curve
(Fig. 1(b)) leading to the greatest mean relative error
obtained for this case study (MRE21.0%). The
extremely low sorption levels w1 encountered for this
particular system at low activities is most likely
responsible for an inadequate estimation of the binary
interaction parameters occurring with a model which
diverges for w1!0. In fact, the modelling of the same
sorption isotherm without the rst experimental point,
which corresponds to an extremely low sorption level
(w10.0006), leads to a mean relative error of 13%
which is a signicant improvement in the modelling
efciency. The same general trend could then be found
using UNIFAC-FV rather than UNIQUAC. It thus
seems the non-linear regression of this very sharp
isotherm in the low activity range provides values
for the binary interaction parameters which cannot
accurately account for the sorption behaviour in the
very high activity range.
Contrary to what was obtained for the former
systems, the sorption of ETBE in the polyetheruretha-
neimide PTMG650-MDI-AP leads to a very smooth
 21 RSSE1000 MRE (%)
0.296 104 17.5
0.269 100 17.3
0.158 169 21.0
0.148 163 20.7
0.738 0.8 2.4
1.987 0.9 2.4
convex isotherm. UNIQUAC as well as UNIQUAC-
FV both provide a very good description of the sorp-
tion isotherm over all the activity range with mean
relative errors of 2.4% (Fig. 1(c) and (f)).
5.2. Sorption of ethyl acetate (AcOEt) (Table 5)
Ethyl acetate is more polar than ETBE and should
thus display stronger dipolar interactions with the
polar polymer materials investigated. The different
sorption isotherms reported in Fig. 2 indeed show a
greater afnity of ethyl acetate towards polyuretha-
neimides compared to ethyl-tert-butyl ether.
The sorption of ethyl acetate in both of the
polyetherurethaneimides PPG725-MID-AP and
PTMG650-MDI-AP can very well be accounted for
by UNIQUAC with mean relative errors of 1.9% and
3.2%, respectively. A slight improvement can even be
obtained with UNIQUAC-FV providing a mean rela-
tive error which can be as low as 1.05% for the system
AcOEt/PPG725-MDI-AP (Table 5).
Compared with ethyl alcohol and ethyl-tert-butyl
ether, the ethyl acetate ester is readily absorbed by the
polyesterurethaneimide PCL1250-MDI-AP. The sorp-
tion process is most likely favoured by the similarity
of the penetrant chemical structure to the PUI poly-
ester soft phase. Here again, UNIQUAC is shown to
really well apply over all the activity range which can
be investigated during sorption experiments (a<0.95;
MRE4.9%). If free volume effects are taken into
account by the corrective term of UNIQUAC-FV, the
modelling is a little better with a mean relative error of
4.7%. The preference for UNIQUAC-FV in this par-
ticular case can however be questioned in regard to the
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141 133

Table 5
Modelling of the sorption of ethyl acetate in polyurethaneimides at 308C by UNIQUAC and UNIQUAC-FV

Sorption of AcOEt at 308C

 12  21 RSSE1000 MRE (%)

PPG725-MDI-AP UNIQUAC 0.282 1.805 1.4 1.9

UNIQUAC-FV 0.052 2.718 0.5 1.0

PCL1250-MDI-AP UNIQUAC 1.539 0.313 15 4.9

UNIQUAC-FV 1.890 0.300 14 4.7

PTMG650-MDI-AP UNIQUAC 0.882 0.796 4.1 3.2

UNIQUAC-FV 0.137 2.366 2.0 2.2
 12 and  21 are the binary interaction parameters. RSSEresidual sum of squares of errors. MREmean relative error.

very slight improvement obtained with a model which
requires two more physico-chemical parameters (i.e.
the pure component densities) compared to the initial
UNIQUAC approach.
5.3. Sorption of ethanol (EtOH) (Table 6)
Ethanol is a protic species which has been shown
to involve strong specic interactions with polyur-
ethaneimides by hydrogen bonding [30,31]. For this
particular penetrant, not only UNIQUAC and
UNIQUAC-FV but also specic UNIQUAC-type
models accounting for hydrogen bonding are to be
assessed for sorption modelling (Table 6).
Both of the isotherms related to ethanol sorption in
PPG725-MDI-AP and PCL1250-MDI-AP at 308C
show very low sorption levels in the low activity
range. The sorption modelling by UNIQUAC and
UNIQUAC-FV provides a very good description over
almost the entire activity range (i.e. for activities up to
and including 0.9). However, a signicant deviation is
found for the highest activities in a similar way as what
could be observed for the ETBE sorption modelling in
the same polymers. All of these solvent polymer
systems have in common the same pattern of very
low sorption levels at low vapour activity. In fact,
as shown by the different isotherms displayed in
Figs. 13, the lower the sorption levels at low activity,

Table 6
Modelling of the sorption of ethanol in polyurethaneimides at 308C by UNIQUAC and related models

Sorption of EtOH at 308C

 12  21 RSSE1000 MRE (%)

PPG725-MDI-AP UNIQUAC 1.442 0.232 57 13.4

UNIQUAC-HB 1.710 0.043 40 11.1
UNIQUAC-FV 1.846 0.203 51 12.8
UNIQUAC-FVHB 2.228 0.054 48 12.3

PCL1250-MDI-AP UNIQUAC 1.662 0.116 42 13.1

UNIQUAC-HB 1.640 0.016 17 10.8
UNIQUAC-FV 2.211 0.104 36 12.5
UNIQUAC-FVHB 2.497 0.020 25 11.8

PTMG650-MDI-AP UNIQUAC 0.577 0.845 5.6 4.3

UNIQUAC-HB 0.964 0.290 5.5 4.2
UNIQUAC-FV 0.031 2.587 4.5 4.0
UNIQUAC-FVHB 0.526 3.839 4.3 4.0
 12 and  21 are the binary interaction parameters. RSSEresidual sum of squares of errors. MREmean relative error.
134 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141

Fig. 2. Sorption of ethyl acetate in polyurethaneimides at 308C. Organic vapour activity vs. weight fraction of solvent in the swollen
membrane. *: experimental data. Modelling curves calculated by UNIQUAC (a)(c) or UNIQUAC-FV (d)(f).

the greater the deviation between the experimental and
calculated data in the very high activity range. This
could be a further point in favour of the assumption
made in a former section, i.e. these very low sorption
levels could be responsible for an inadequate estima-
tion of the binary interaction parameters for models
which diverge numerically for extremely low sorption
levels.
The polyurethaneimide PTMG650-MDI-AP is
much more sensitive towards ethanol sorption than
the former PUIs in the low activity range (Fig. 3(c))
and UNIQUAC as well as UNIQUAC-FV both pro-
vide a very good modelling over all the activity range
as shown in Fig. 3(c) and (f) (mean relative errors less
than 4.5%).
We now consider UNIQUAC-type models which
have been derived specically to account for hydrogen
bonding to assess whether or not they can give a
further improvement in comparison with UNIQUAC
and UNIQUAC-FV. As shown by the error estimates
reported in Table 6, UNIQUAC-HB compared to
UNIQUAC usually leads to a signicant decrease in
the residual sum of squares of errors whatever the
polymer investigated (from 30% to 60% except
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141 135

Fig. 3. Sorption of ethanol in polyurethaneimides at 308C. Organic vapour activity vs. weight fraction of solvent in the swollen membrane. *:
experimental data. Modelling curves calculated by UNIQUAC (a)(c) or UNIQUAC-FV (d)(f).

for the system EtOH/PTMG650-MDI-AP for
which both of the models provide very good error
estimates). As a result, the corresponding mean
relative errors lose 12 points. The comparison
between the relative improvements provided by
taking into account either free volume effects
(UNIQUAC-FV) or hydrogen bonding (UNIQUAC-
HB) shows that the inuence of hydrogen bonding
could prevail on the free volume effects for ethanol
sorption the different polyurethaneimide elastomers.
Indeed, UNIQUAC-HB generally proves its super-
iority towards UNIQUAC-FV especially for the sys-
tems for which the initial UNIQUAC approach was the
less accurate.
A further logical step for the modelling of the
sorption of protic species in elastomers containing
HB acceptor sites was the testing of a model which
would account for free volume effects (which are
believed to be important especially for elastomers)
as well as hydrogen bonding. The derivation of such a
model from the different approaches reported in the
literature is straightforward and leads to the
UNIQUAC-FVHB model as described in Sec-
tion 3.4). Compared with UNIQUAC and
136 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141

Fig. 4. Sorption of ethanol in polyurethaneimides at 308C. Organic vapour activity vs. weight fraction of solvent in the swollen membrane. *:
experimental data. Modelling curves calculated by UNIQUAC (a)(c) or UNIQUAC-FV (d)(f).

UNIQUAC-FV, this new approach is slightly better in 6. Discussion

terms of modelling efciency (Table 6). As could be
expected from the model mathematical form, it still
suffers from a slight discrepancy between experimen-
tal and calculated data in the very high activity range
for polymers almost insensitive towards ethanol in the
low activity range (Fig. 4(d) and (e)). However,
UNIQUAC-FVHB does not yield any signicant
improvement compared to UNIQUAC-HB. This is
most likely due to an effect of accumulation of errors
and also to the fact that hydrogen bonding seems to
prevail on free volume effects for these particular
systems.
6.1. Performance of the UNIQUAC-type models
(Table 7)
In this part, a transversal comparison is made to
help draw a few general guidelines about the choice of
one particular model for a given system.
Note: In Table 7, the error estimates in terms of
residual sum of squares of errors (RSSE) have been
reported for the four UNIQUAC-type models thus
including UNIQUAC-HB and UNIQUAC-FVHB
even for the aprotic solvents ETBE and AcOEt. For
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141
Table 7
Combined error estimates for the modelling by UNIQUAC and related models for the sorption of solvents of moderate to strong polarity in
PPG725-MDI-AP, PCL1250-MDI-AP and PTMG650-MDI-AP at 308C
ETBE
RSSE1000
UNIQUAC 274
UNIQUAC-HB (274)
UNIQUAC-FV 264
UNIQUAC-FVHB (264)
RSSEresidual sum of squares of errors.
these particular species, q0 reduces to q. Therefore,
UNIQUAC-HB and UNIQUAC-FVHB are strictly
equivalent to UNIQUAC and UNIQUAC-FV, respec-
tively. Consequently, the corresponding error esti-
mates are only given to allow the estimation of the
overall RSSE based on the complete set of solvent
polymer systems investigated, and thus a comparison
between the different approaches.
Based on the error estimates obtained for the sorp-
tion modelling of ETBE, AcOEt and EtOH in three
polyurethaneimide elastomers (Table 7), accounting
for free volume effects by UNIQUAC-FV system-
atically slightly improves the sorption modelling com-
pared to UNIQUAC. This is in good agreement with
the conclusions of former related studies [14,24,35].
However, the use of this more rened model requires
two additional physicochemical parameters for the
pure components be known which is not always the
case for many solvent polymer systems. This require-
ment somewhat restricts the applicability of
UNIQUAC-FV despite a better overall performance.
The modelling of the ethanol sorption in three
elastomers containing HB acceptor sites showed the
overall superiority of UNIQUAC-HB for these parti-
cular systems. Though based on a small number of
representative cases, the conclusion well agrees with
former studies on thermodynamics of small molecules
[26,29]. This is therefore an interesting approach as
also previously reported by Heintz and Stephan [19]
for solvent polymer systems displaying very strong
interactions by hydrogen bonding. For the systems
based on ethanol in this work, this approach is shown
to be more efcient than UNIQUAC, UNIQUAC-FV
and even UNIQUAC-FVHB (Table 7), making
UNIQUAC-HB a model of choice for these particular
systems. An extension of this study to other protic
137
AcOEt EtOH
RSSE1000 RSSE1000  RSSE1000
20.5 105 399
(20.5) 62.5 357
16.5 91.5 372
(16.5) 77.3 358
penetrants would certainly be very interesting to con-
rm the generality of this point.
6.2. UNIQUAC-type models vs. the FloryHuggins
and ENSIC models (Table 8)
At the present stage, not very common are still the
sorption models which are not only restricted to binary
solvent polymer systems but can also be readily
extended to multicomponent solvent polymer systems
of higher orders (i.e. ternary, quaternary systems, etc.).
UNIQUAC and the related models [18,19,22,36], the
FloryHuggins model [3,6,37,38] and the ENSIC
approach [10] have been chosen for this evaluation
because they have been shown, at least theoretically, to
be extendable to multi-component phase equilibria for
solvent polymer systems and this potentiality is
clearly an advantage compared to other more basic
approaches.
The FloryHuggins theory [1,2] was initially
derived for describing the sorption of small molecules
in polymer networks. Based on a rather simple lattice
concept and relatively drastic assumptions which
should theoretically restrict its application to apolar
systems [3], this reference theory has been used for a
wide range of systems even including systems of
rather strong polarity. This wide use has been mainly
promoted by the relative simplicity of the model
which, at least theoretically, allows the sorption mod-
elling by a single parameter known as the FH inter-
action parameter :
ln a ln  1  1 2 : (17)
Applied to the nine isotherms considered here, this
model only enabled the tting of those involving the
polymer PTMG650-MDI-AP [32] and thus led to a
138 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141
Table 8
Combined error estimates for the modelling by FloryHuggins and the ENSIC model for the sorption of solvents of moderate to strong polarity
in PPG725-MDI-AP, PCL1250-MDI-AP and PTMG650-MDI-AP at 308C [32]
ETBE
RSSE1000
FloryHuggins 943
ENSIC model 1.4
RSSEresidual sum of squares of errors.
high overall error estimate (RSSE1775) (Table 8).
Therefore, compared to the different UNIQUAC type
models, the FH theory can be considered as much
poorer for solvent polymer systems of moderate to
strong polarity despite its rather common relevance to
more simple systems.
Though also based on a lattice concept, the ENSIC
(acronym standing for ENgaged Species Induced
Clustering) model derives from a very different
approach which considers the sorption phenomenon
as a purely mechanical anisotropic process [10,11].
This recent approach leads to the following relation:
 
kp
 expks kp a 1; (18)
ks kp
where the model key parameters kp and ks are thus
related to the afnity of a penetrant molecule towards
a polymer site and another sorbed molecule, respec-
tively.
Applied to the sorption of ETBE, AcOEt and EtOH
in the three polyurethaneimide elastomers considered
in this work, the ENSIC model again proved its out-
standing efciency over all the activity range whatever
the system investigated (Table 8) [32]. This point must
be stressed in regard to the specic problem encoun-
tered with other models which diverge for extremely
low sorption levels (w1!0) in the low activity range.
As reported in a previous work [32], this model gives
correlation coefcients in the very high range (up to
0.9996) and enables an excellent tting whatever the
penetrant polarity (i.e. from rather low polarity for the
ether compound to fairly high polarity for ethanol) and
even for systems involving strong specic interactions
by hydrogen bonding.
Compared to UNIQUAC and related models, the
ENSIC model leads to an overall residual sum of
squares of errors (RSSE0.0027) which is by far
AcOEt EtOH
RSSE1000 RSSE1000  RSSE1000
155 677 1 775
0.3 1.0 2.7
the best for the nine binary solvent polymer systems
investigated (Table 8). This is clearly an advantage for
this model which is in addition much simple than the
UNIQUAC and related approaches for binary solvent
polymer systems.
7. Conclusion
Despite a recent signicant increase in the number
of investigations dealing with UNIQUAC and
UNIQUAC related models for solvent polymer phase
equilibria, quite a lot of work still remains to be done
to get a clear picture about which model should be
preferred for a particular system.
In this work, UNIQUAC and related models were
systematically assessed for their ability to deal with
systems of ever increasing complexity. In addition to
the initial UNIQUAC model, three related models
could account for:
(i) free volume effects which are believed to be
signicant especially for elastomer materials:
UNIQUAC-FV;
(ii) hydrogen bonding which has been shown to be a
key factor for the sorption of protic solvents in poly-
mers containing HB acceptor sites: UNIQUAC-HB;
(iii) the combination of both of these effects:
UNIQUAC-FVHB.
Tested on systems involving elastomers and
vapours of moderate to strong polarity, the modied
UNIQUAC models were generally found more accu-
rate than the initial UNIQUAC model.
Generally, UNIQUAC-FV proved its superiority for
the sorption of aprotic species (ether, ester) in poly-
urethaneimides which are elastomers for which free
volume effects are believed to be signicant.
A different conclusion could be drawn from the
investigation of systems involving protic species (i.e.
 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141 139

HB donor species) and elastomers containing HB aFV

i activity from free volume contribution
acceptor sites. For these particular systems, it seems (dimensionless)
the hydrogen bonding contribution prevails on free aRi activity from residual contribution (dimen-
volume effects and UNIQUAC-HB provides a better sionless)
description than UNIQUAC-FV. A further logical step aiR-HB activity from residual contribution (UNI-
which considers the combination of both of these QUAC-HB) (dimensionless)
effects for these HB acceptor elastomers is shown k probabilistic insertion parameter (dimen-
to yield no further improvement compared to sionless)
UNIQUAC-HB most likely due to effects of accumu- Mi molecular weight of component i (g/mol)
lation of errors and/or the predominance of hydrogen qi relative surface parameter (UNIQUAC)
bonding for these systems. (dimensionless)
Compared with the other few approaches which can q0i modified relative surface parameter (UNI-
be extended to multi-component phase equilibria, the QUAC-HB) (dimensionless)
UNIQUAC and related models were found to be much ri relative volume parameter (UNIQUAC)
more accurate than the FloryHuggins (FH) model (dimensionless)
which is nevertheless still widely used in the literature wi weight fraction of component i (dimension-
mainly owing to its much greater simplicity. Another less)
approach theoretically extendable to multi-component xi molar fraction of component i
systems, i.e. the ENSIC model, revealed itself much z coordination number (z10.0)
more efcient than UNIQUAC-type models with
extremely low tting errors for the binary systems Greek symbols
investigated. Therefore, this simple mechanistic
approach can be considered as a very good alternative  FloryHuggins interaction parameter (di-
to more complex models when dealing with vapour mensionless)
sorption in polymer systems. i volume fraction of component i (dimen-
However, at the present stage, UNIQUAC and sionless)
related approaches are the only ones to have already i density of component i (g/ml)
shown a very high potential for multi-component  ij binary interaction parameter (UNIQUAC)
systems involving a polymer phase on the basis of (dimensionless)
binary parameters only, i.e. without requiring higher i surface fraction of component i (dimen-
order (and thus additional) parameters [18,19,22,36]. sionless)
In addition, they have the outstanding advantage to 0i modified surface fraction of component i
enable a full prediction of multi-component equilibria (dimensionless)
within the frame of UNIFAC, provided all the incre-
ments required for the group contribution method be Abbreviations
known which is usually the case for most of the
systems investigated. This can clearly speak for ABS absolute value
UNIQUAC and related models despite their greater AP pyromellitic anhydride
complexity and a slightly poorer efciency, when AcOEt ethyl acetate
compared to the ENSIC model for binary solvent ETBE ethyl-tert-butyl ether
polymer system involving moderate to strong inter- EtOH ethanol
actions. FV free volume
HB hydrogen bonding
8. List of symbols PCL polycaprolactone diol
PE polyethylene
ai activity of component i (dimensionless) PEBA polyether-block-amide
aCi activity from combinatorial contribution PEG polyethylene glycol
(dimensionless) PIB polyisobutylene
140 A. Jonquieres et al. / Journal of Membrane Science 150 (1998) 125141

PMA polymethylacrylate [10] E. Favre, R. Clement, Q.T. Nguyen, P. Schaetzel, J. Neel,

PP polypropylene
PPG polypropylene glycol
PS polystyrene
PU polyurethane
PUI polyurethaneimide
PVA polyvinylalcohol
PVAc polyvinylacetate
RSSE residual sum of squares of errors
MDI methylenediphenyldiisocyanate
MRE mean relative error
Acknowledgements
Financial support provided by the Centre National
de la Recherche Scientique (CNRS) within the fra-
mework of an interdisciplinary scientic program
(PIRGP TRANSFERTS T8) is gratefully acknowl-
edged.
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