Journal of Membrane Science 320 (2008) 42–56

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Journal of Membrane Science

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Permeation of gases through microporous silica hollow-fiber membranes:

Application of the transition-site model
Philip Molyneux ∗
Macrophile Associates, 33 Shaftesbury Avenue, Radcliffe-on-Trent, Nottingham NG12 2NH, UK

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

Article history: In a previous paper [P. Molyneux, “Transition-site” model for the permeation of gases and vapors through
Received 29 September 2007 compact films of polymers, J. Appl. Polym. Sci. 79 (2001) 981–1024] a transition-site model (TSM) for the
Received in revised form 1 February 2008 activated permeation of gases through compact amorphous solids was developed and applied to organic
Accepted 2 March 2008
polymers; the present paper examines the applicability of the TSM to permeation through microporous
Available online 18 March 2008
silica. The basis of the TSM theory for amorphous solids in general is outlined; the present extension to
inorganic glasses has revealed that the transition sites (TS) of this theory, which are the three-dimensional
Keywords:
saddle-points critical in the molecular sieving action, equate to the doorways long recognized in per-
Activation energy
Hollow-fiber membranes
meation through amorphous silica and other inorganic glasses. The TSM, which views permeation as a
Microporous silica primary process, is contrasted with the conventional sorption–diffusion model (SDM) for permeation. It is
Molecular sieving pointed out that in the SDM, the widely accepted analysis into two apparently distinct factors – sorption
Permeability theory (equilibrium) and diffusion (kinetic) – has the fundamental flaw that these factors are not independent,
Transition-site doorways since both involve the sorbed state. By contrast, the TSM focuses on the permeant molecule in only
two states: as the free gas, and as inserted in a doorway D; hence the characteristics of these doorways
– (unperturbed) diameter  D , spacing , and the thermodynamic parameters  (force constant) and 
(entropy increment) for the insertion process – can be evaluated. The theory is applied to literature data
[J.D. Way, D.L. Roberts, Hollow fiber inorganic membranes for gas separations, Sep. Sci. Technol. 27 (1992)
29–41; J.D. Way, A mechanistic study of molecular sieving inorganic membranes for gas separations, Final
Report submitted to U.S. Department of Energy under contract DE-FG06-92-ER14290, Colorado School of
Mines, Golden, CO, 1993, www.osti.gov/bridge/servlets/purl/10118702-ZAx4Au/native/1011872.pdf; M.H.
Hassan, J.D. Way, P.M. Thoen, A.C. Dillon, Single component and mixed gas transport in silica hollow fiber
membrane, J. Membr. Sci. 104 (1995) 27–42] on the permeation through microporous silica hollow-fiber
membranes (developed by PPG Industries Inc.) of the nine gases: Ar, He, H2 , N2 , O2 , CO, CO2 , CH4 and
C2 H4 , over the temperature range 25–200 ◦ C. The derived Arrhenius parameters for the permeation of
these gases (excepting He) lead to estimates of the four doorway-parameters:  D , 125 pm; , ca. 30 nm;
, 0.43 nN; , 1.7 pN K−1 ; these values lie within the ranges of those obtained with the glassy organic
polymers. Some “secondary effects”, shown particularly by CO and CO2 , are interpreted as host–guest
interactions at the doorway. The behavior of He is anomalous, the permeation rising linearly with tem-
perature. This study confirms that the TSM may be applied to gas permeation by activated molecular
sieving for this type of inorganic membrane.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
The migration of gases in and through solids has many prac-
tical and theoretical implications, particularly in the use of films
as barriers, and in separation processes [1,2]. In these processes,
we can distinguish permeation as the transfer of the gas through a
layer of the solid; solubility or sorption as the equilibrium process
∗ Tel.: +44 115 933 4813; fax: +44 115 933 4813.
E-mail address: molyneux@easynet.co.uk.
between the gas and that held within by the solid; and diffu-
sion as the movement of the sorbed gas molecules within the
solid.
In current thought, the primacy in migration is given to diffusion
[3–6]. With solubility as the equilibrium-based process, perme-
ation is then viewed as the composite of solubility and diffusion,
leading to the sorption–diffusion model (SDM). By contrast, in a
previous paper [7] dealing with migration of gases and vapors
in organic polymers, a model is presented which gives primacy
to permeation; this was termed the transition-site model (TSM).
In the present paper this model is applied to simple gases per-

0376-7388/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2008.03.001
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56 43

meating through a microporous form of amorphous silica, using
literature data on hollow-fiber membranes. Because of the nov-
elty and unusual approach of the TSM, it is useful to firstly outline
the theory and its general application (Sections 2.1–2.5), and then
the results of its application to organic polymers (Sections 2.6–2.7),
before considering its specific application to permeation through
silica (Section 3). The values of absolute entropy and molecular
diameter required in the treatment of the experimental data are
also discussed (Appendixes A and B).
2. The transition-site model for permeation
2.1. Lattice picture of the migration process
To illustrate the relations and concepts dealt with in this paper,
Fig. 1 shows the main features of the lattice picture that is used
in the SDM and has likewise been adopted for the present TSM.
The migration process requires there to be “free volume” regions
that take up the sorbed guest molecules, and that interconnect via
more restricted locations. For an amorphous isotropic solid, these
will be located and oriented statistically through the bulk of the
solid, as fixed in position when (for example) the material solid-
ified. However, as shown in Fig. 1, for mathematical tractability
this may be replaced by a cubic lattice (lattice parameter ), with
the yz plane as the plane of flux, and the migration taking place
down the x-axis in the direction of the concentration gradient in
the solid and the pressure difference across it. In a full picture,
there would be extensions of these lattice features into the y- and
z-directions.
Combining this with the solubility equilibrium for the inser-
tion of the molecule into the sorption site trough at (or near)
the “upstream” surface, and likewise for the desorption from the
“downstream” face of the membrane, gives the potential energy
profile shown in Fig. 1B. Here it is assumed that the sorption process
is exothermic; however, the picture discussed is not importantly
altered if this sorption process is endothermic. On the SDM, the
migration then takes place by a series of activated jumps between
successive locations of the sorbed molecules.
This lattice picture is well established, originating apparently
with the pioneering work of Barrer on activated migration in
diverse media [8,9] and used since then in numerous molecular
modeling studies [10–14]. In fact, the lattice picture used here mim-
ics that of interstitial migration in crystalline solids (for example,
atomic species such as H, C and N in crystalline Fe); however, the
present TSM does not seem to have been applied to such processes
[4,6].

Fig. 1. Schematic of the activated diffusion and permeation processes for an amorphous solid film (thickness L), showing the four environments for the permeant gas molecule
G: , molecule in the upstream gas phase at pressure p0 ; , sorbed molecule; , molecule in transition-site doorway D; , molecule in the downstream gas phase, at
pressure pL . (A) Pressure gradient: linear gradient of pressure px (at general depth x) within the film (ideal permeation for low p). (B) Energy profile: The amorphous solid
is modeled by a cubic lattice (spacing ), with yz (perpendicular to the plane of the diagram) as the plane of flux, and with migration occurring in the x-direction (left to
right). The troughs are the preferred sorption sites, and the peaks are the transition-site doorways D. Ordinate energy axis indicates the enthalpy change of sorption HS , the
diffusion activation energy ED and the permeation activation energy EP . (C): “Free volume” and “doorways”: Sequence of environments across the film—permeant molecule
diameter  G and unperturbed transition-site doorway diameter  D as labeled; the complete lattice would have corresponding features in the y- and z-directions.
44 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
In parallel with the energy profile shown in Fig. 1, there must
also be an entropy profile; this is seldom considered, but evidently
must be taken into account to give the true, free energy descrip-
tion of the processes involved. In this case, the profile would have
troughs where molecules are restricted; a further difference is that
in contrast to the energy situation where the energy level is zero for
all dilute gases, in the case of entropy the starting levels would be
different following the absolute entropies of the gases considered.
This has to be taken into account in interpreting the van’t Hoff and
Arrhenius prefactors as discussed below. In previous cases where
entropy effects have been considered [9,10,14], they have dealt only
with the diffusive jump process.
2.2. General relations
On the basis of “ideal conditions” that is, low pressure p of
the permeant gas and low concentration c of dissolved perme-
ant, the three determining parameters—the Henry’s Law solubility
coefficient, S,1 the diffusion coefficient D, and the permeability
coefficient P are related [2] by
P = DS.
It is this equation that is used as the basis for the conventional
SDM, which considers that permeation must be a composite quan-
tity, depending on both the sorptive and the diffusive properties of
the system.
In considering the molecular bases of these processes, the
temperature dependence of the three parameters is of particular
importance. These generally take the similar van’t Hoff (sorption)
and Arrhenius (permeation and diffusion) forms. In the light of Eq.
(1), this gives for the corresponding prefactors
P0 = S0 D0
and for the energy quantities
EP = HS + ED
where EP and ED the activation energies for permeation and diffu-
sion, and HS is the isosteric enthalpy change of sorption.
In Eq. (3), if the sorption process is exothermic (so that
HS is negative), then the value of the permeation activation
energy EP becomes the difference between the numerical values
of HS and ED ; for example, in the case of H2 O with poly(ethyl
methacrylate) (PEMA), the studies of Stannett and Williams [15]
gave HS = −34 kJ mol−1 (exothermic) and ED = 36 kJ mol−1 so that
EP = 2 kJ mol−1 (compare Fig. 1B).
As a general point, inasmuch as each permeant has spe-
cific Arrhenius and van’t Hoff parameters, the plots for different
permeants may cross. This is particularly important with the
increasing emphasis on the use of membranes over wide tempera-
ture ranges. For example, the recent work of Wilks and Rezac [16]
showed, for the competitive permeation of CO2 and H2 through
poly(dimethylsiloxane) (PDMS) membranes, that the selectivity
factor is 4.2 at 35 ◦ C (CO2 faster), but that this has fallen to 0.8 (H2
faster) at 200 ◦ C. Thus the comparison of the permeation behav-
ior at a single temperature is not sufficient to elucidate migration
behavior.
Furthermore, any molecular interpretation should seek to
explain and correlate not only the activation energy, but also the
prefactor. In particular, using the TSM [7], valuable information is
1
This symbol for solubility coefficient, used here in conformity with customary
practice, should not be confused with that for entropy (S0 , etc.) used later in the
paper.
obtained from P0 on the entropy effects in the migration process,
and on the spacing  between transition-sites (Fig. 1).
A more general point in connection with these energy levels is
that they allow the permeation activation energy EP to be zero or
negative if ED becomes equal to or less than HS , so long as ED has
a positive value as required for the jump process.
2.3. Critique of the sorption–diffusion model (SDM) for analyzing
permeation
The conventional and widely accepted belief is that permeation
must be considered as composite, that is, the resultant of sorption
(equilibrium) and diffusion (kinetic) effects. This seems to be sup-
ported, for example, by the form of Eq. (1), and by the simplicity of
the units for diffusion coefficient (m2 s−1 ) compared with those for
permeability coefficient (mol m m−2 s−1 Pa−1 ).
However, as detailed in the previous paper [7], there are a num-
ber of instances where permeation is a simpler process than would
be expected if it were the composite of independent effects. In this
section, this is taken a step further by showing that, despite the
almost universal view that diffusion must be considered as the pri-
(1) mary process in solid-state migration, there are a number of aspects
that raise doubts as to its validity for this purpose. These may be
considered under three headings.
2.3.1. The sorption and diffusion processes are not independent
The primary point of weakness of the SDM arises in the uni-
versally assumed analysis of permeation into the two assumedly
distinct aspects, sorption (equilibrium factor) and diffusion (kinetic
factor). Any analysis of a physical or chemical process requires that
the proposed component effects are independent; for example, in
analyzing the factors controlling the volume of a fixed amount of an
(2) ideal gas, these two factors would be the pressure and the (absolute)
temperature, each of which may be varied independently. However,
in the case of the SDM, the two coefficients S and D are clearly not
independent, since they both involve the sorption state. For the
(3)
sorption coefficient S relates to the equilibrium between the gas
state and the sorption state; while the diffusion coefficient D relates
to the ease of a jump from the sorption state across the intervening
barrier (doorway), or (on transition-state theory) to the equilibrium
between the sorption state and the transition state (Fig. 1B).
Of course, this is not to argue against the classical picture of
permeation being a sequence of processes that we call “sorption”,
“diffusion” and “desorption”; nor is it to argue with the mathemat-
ical validity of Eq. (1). But neither of these leads to, or necessarily
requires, the conventional SDM analysis.
2.3.2. The sorption sites are heterogeneous
Considering the sorption of a single simple-molecule permeant
in an amorphous solid, such as an organic polymer, or an inorganic
glass, because of the disordered molecular structure of the host
matrix, the permeant molecules will be held in a variety of sites
and locations. For example, the variation of solubility and partial
molar volume with uptake indicates a Gaussian distribution for the
sorption sites both with glassy organic polymers [17a] and with
vitreous silica [17b]. It is therefore evident that the starting point
for the diffusive jump (Fig. 1) is not well defined.
2.3.3. It is the pressure gradient and not the concentration
gradient that is the true driving force for transport
The deficiencies in taking the concentration gradient as the
driving force, are seen from the molecular viewpoint, when we
compare the behavior of two permeants O2 and H2 O, which have
similar molecular diameters (293 pm and 289 pm from critical
constants—see Appendix A and Ref. [7]), in a polar polymer such as
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
PEMA [15]. For a given partial pressure of the penetrant, the uptake
of the H2 O is much greater than that of the O2 because the H2 O will
hydrogen bond to the ester groups in the polymer chains. However,
for the same concentration gradient, the actual amount of H2 O free
for diffusion will be much smaller than that for the O2 , because of
this hydrogen bonding. Thus the use of the concentration gradient
clearly does not represent the true driving force for the migration
process.
In this example, where the structures and interactions for the
solid and the migrant molecule are well established, the molecular
basis is self-evident, but it must apply more generally where these
forces may not be well understood.
These objections do not apply when we consider the pressure
gradient as the driving force, since this is a true measure of the
gradient of chemical activity (Fig. 1A). The present TSM uses this
picture, and shows how this gradient may be linked to the migration
process.
The validity of the pressure gradient as the driving force
is revealed in numerous cases where, when the conditions are
changed, the values of D and S vary markedly but that of P remains
essentially constant. Since the sorbed state enters in opposite ways
in the sorption and diffusion processes, its effect cancels out in
permeation.
For example, considering a case with the same permeant in the
same solid at different pressure and concentration levels, Rundgren
et al. have shown recently [18] with H2 /vitreous silica at 550 ◦ C, that
when the upstream pressure was varied up to 0.12 MPa, the value
of P remained essentially constant (±10%) although the value of S
decreased by a factor of approximately three while that of the dif-
fusion coefficient D correspondingly increased by the same factor.
Much the same effect can apply to the same permeant in differ-
ent solids, as with the case of H2 O in moderately polar polymers
previously discussed [7]. A striking example of this type of effect
is shown in the work of McCall et al. [19] on the permeation of
H2 O through poly(ethylene) (PE) films that had been air-oxidized
in processing to varying extents, leading to the incorporation of
hydrophilic groups on the polymer chains; such oxidation up to
3% combined oxygen gave a 50-fold increase in the sorption coeffi-
cient S compared with the starting PE, but an essentially equivalent
decrease in the diffusion coefficient D, so that the permeability
coefficient P was essentially unchanged (±20%) by the oxidation.
The above arguments apply not just to organic polymers or vit-
reous silica from which the examples have been chosen, but to any
system where the SDM analysis is currently used.
2.4. Analysis of the jump process
In the field of migration through organic polymers, little atten-
tion has been paid to the nature of the peak on the path of the
jump, with greater attention being paid to the “free volume” which
relates to the environment of the sorption sites [2]; however, the
previously developed TSM [7] focuses particularly on the state of
the permeant molecule at this peak. It turns out, that in the field
of migration in inorganic glasses, these transition sites have been
recognized for over half a century, and were termed doorways [20],
a name that has been retained since [21–25]. It is therefore conve-
nient to use term doorway (D) interchangeably with transition-site
(TS) in the rest of the paper.
A simple analysis of the jump process further highlights the
significance of the TS doorway. Firstly, if we apply the Principle
of Microscopic Reversibility to a jump, it follows that the reverse
process must also be acceptable as a jump; thus on the average
the jump will be symmetrical about the midpoint. Secondly, the
requirement for activation of the molecules to enable the jump to
take place indicates the presence of an energy barrier, which would
45
be located on the average at this midpoint. Finally, because of the
Boltzmann factor exp(−E/RT) that controls the fraction of perme-
ant molecules with the required excess energy E, in making the
jump the penetrant molecule will expend the minimum amount of
energy necessary for a successful jump, that is, barely passing over
the central point. This location is the transition-site doorway D,
which has the nature of a three-dimensional saddle-point (Fig. 1B
and C).
2.5. Derivation of equation for permeability coefficient on the
TSM
The present TSM is then a direct application of the well-
established standard theory of the transition state (also termed the
activated complex) for chemical reactions [26]. For an elementary
chemical reaction, there is postulated to be equilibrium between
the starting reactants and those in the transition state, this being
the position of maximum potential energy on the lowest energy
path from the reactant to the products; this transition state then
converts into the products of the reaction (or may revert to the
reactants). For example, for the transfer of the atom B between the
species A and BC, the two-step sequence involved is:
A + B − C  [A· · ·B· · ·C] ‡  [A − B + C]. (4)
Reactants Transition state Products
Although this picture is well accepted for reactions in the gas
phase, there is some hesitation in applying it to processes in con-
densed phases. However, it is well established as the explanation of
the primary salt effect for reactions in aqueous solution, that is, the
effect on the rates of reactions between ions in solution of added
“neutral salt” (an electrolyte with non-common ions); here it is the
net charge on the transition state that is important, and this state is
evidently sufficiently long-lived for the Debye–Hückel ionic atmo-
sphere from the added neutral salt to be established [26]. Moreover,
the theory has been applied successfully in considering perme-
ation in physiological systems [27], while the concept of “transition
state analogs” in now widely used in enzyme chemistry [28]. More
specifically, this type of picture was used some time ago to inter-
pret quantum effects in the permeation of “light” gases (He, H2 ,
D2 ) through organic polymers [10], and more recently to similar
systems using molecular dynamics simulations [29].
With permeation through an amorphous solid, the pressure dif-
ference p across the layer of solid also corresponds to a gradient of
partial pressure of the gas within the solid, representing a gradient
of chemical activity across the layer. For the ideal case under present
discussion (dilute gases, and dilute solutions of the penetrant in
the solid, so that there is no “plasticization” or other modification
of the host solid by sorbed permeant), this gradient will be linear
(Fig. 1A). Concretely, the partial pressure at any level would be that
within a microscopic cavity at that level; alternatively, it would be
the pressure realized if the solid were sliced through in the yz-plane
at that level, the two parts slightly separated, and the permeation
flux resumed. This does not mean that there are actual free per-
meant molecules in the solid, but simply that any depth x can be
assigned its value of the partial pressure px .
Applying these concepts to the cubic lattice picture having lat-
tice parameter  (Fig. 1), the occupancy of doorways at depth x is
controlled by the insertion equilibrium:
G(x) + D(x)  [GD(x)]‡ (5)
where D(x) is an unoccupied doorway at the depth x, GD(x) is an
occupied doorway at that depth (labeled with the double cross “‡ ”
to show its analogy with the transition state in Eq. (4)), and G(x)
relates to the partial pressure at that level as already discussed.
The rate of loss of G from the occupied doorways (downstream or
46 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56

upstream—Fig. 1B) is then taken to be controlled by the standard [(S(GD) − S(D)] in Eqs. (9), (10) and (13) is the equivalent entropy
transition-state rate coefficient k‡ ≡ kB T/h where kB is the Boltz- change for this same process.
mann constant and h is the Planck constant [26]. On the TSM, it It is useful to analyze the value of EP into three presumably
is this gradient of occupied sites [GD(x)]‡ that gives rise to the independent contributions to the insertion process of Eq. (5):
observed flux in the downstream direction.
EP = EMM + Eex − EMG (14)
This then leads [7] to an expression for the flux that correctly
incorporates its experimentally observed proportionality to the where EMM is the energy to overcome any noncovalent interactions
area, the pressure difference across the film, and the reciprocal of between the host matrix (M) across the unperturbed doorway aper-
the film thickness. The permeability coefficient P then becomes ture, Eex is the energy to expand the matrix by the insertion of
 k T    the (presumably) larger gas molecule G (taken to be a incompress-
B ‡ −U ‡ ible sphere), and EMG is the energy released from any interactions
P= exp(S ) exp (6)
ehNA RT (presumably, noncovalent) between the molecule of G and the sur-
rounding host matrix in the doorway.2 The first contribution, EMM ,
where e is the exponential number, NA the Avogadro constant, S‡
is neglected here, and this is supported by the fact that the door-
the entropy change for the insertion of a mole of the gas G into a
ways are later deduced to have a diameter greater than 100 pm
mole of the doorways D according to Eq. (5), and U‡ is the internal
(Section 3.5).
energy change for this same process. The Arrhenius prefactor and
In previous analyses of this process as applied to silica and
the activation energy then become
derived inorganic glasses, attention has been focused on the second
 k T   
S ‡ contribution Eex . In its earliest development the doorway was con-
B
P0 = exp (7) sidered as a spherical cavity, but this was later replaced [20] by the
ehNA R
somewhat more realistic picture of a cylindrical cavity; this would
EP = U ‡ . (8) then lead, using the mechanics of elasticity for the expansion of a
thick-walled pipe, to the relation
Considering Eq. (7), evidently the prefactor P0 is not expected
GD (G − D )2
to be truly temperature independent since the expression has the Eex = (15)
factor T in front, but over narrow temperature ranges the variation 4
is much less than that of the exponential factor, so that it is per- where G is the shear modulus of the bulk solid,  D the diameter of
missible to use the average temperature in applying this equation. the unperturbed doorway, and  G is the diameter of the permeant
In any case, there may also be a further complicating effect from molecule (see Fig. 1C). However, this commonly applied formula-
changes in S‡ with temperature. tion [18,20–25] suffers from two defects: firstly, the doorway would
The entropy of activation S‡ can be expressed in terms of the be saddle-shaped (Fig. 1C), rather having parallel sides as Eq. (15)
entropies of the “reactants” and “products” for the insertion process requires; and secondly, there is no reason to believe that the elastic
(5) as behavior of the solid at the molecular level (relating to the rotation
and flexion of individual bonds) follows that for the bulk solid as
S ‡ = S(GD) − S(D) − S 0 (G) (9) defined by the shear modulus G.
In many previous formulations [10,18,20–25,29], Eex has been
where S(GD) is the entropy of 1 mol of occupied doorways, S(D) that
equated to the activation energy for diffusion, which ignores the
of the occupied sites, and S0 (G) is the absolute molar entropy of the
part played by the sorption enthalpy in the diffusive jump process
gas. Substituting in Eq. (7) and rearranging gives
(Fig. 1B).
 k T   [(S(GD) − S(D)] 
B Summarizing, in contrast to the diffusive jump picture, in the
P0 exp[(S 0 (G)/R)] = exp . (10)
ehNA R TSM the permeation activation energy is referred to a well defined
initial state, that of the free gas, with reference energy of zero for
It is convenient to define a quantity Y, the entropic coefficient,
any gas (Fig. 1B); however, the prefactor P0 has to be adjusted for the
relating the original permeability coefficient P and the absolute
different absolute entropies of different gases to give the entropic
entropy by
prefactor Y0 according to Eq. (12).
Y ≡ P exp[(S 0 (G)/R)]. (11)
2.6. Application of the TSM to experimental data for organic
Correspondingly, for the limiting case of 1/T → 0, this defines the polymers
entropic prefactor Y0 as
In the previous application of the TSM to organic polymers [7], it
Y0 ≡ P0 exp[(S 0 (G))/R]. (12) was tested on the collected literature data [30] for the permeation
of a variety of gases (ranging from He to SF6 ) with 16 amorphous or
This last expression is used in evaluating Y0 from permeation
semi-crystalline polymers using three test plots, involving the two
experiments, as discussed below. In these expressions for Y and Y0 ,
parameters EP and log Y0 together with the permeant gas molecular
the units of pressure implicit in the absolute entropy and explicit in
diameter  G :
the permeability coefficient have to be brought into concordance,
as discussed in Appendix A. Plot A: EP versus  G
Substituting from Eq. (12) in Eq. (10) and taking logs gives Plot B: log Y0 versus  G
 k T   [S(GD) − S(D)]  Plot C: log Y0 versus EP .
B
log Y0 = log − log  + (log e) . (13)
ehNA R
Previously [7] there had been four test plots, with the first of
As discussed below, this relation is useful in making estimates these (“Case 1”) a direct plot of the original Arrhenius parame-
of the doorway spacing .
Reverting to Eq. (8), the permeation activation EP is revealed as
the internal energy change U‡ to insert the molecule of G into the 2
Kirchheim has shown the importance of this site expansion energy term Eex for
doorway D (Eq. (5) and Fig. 1C). Likewise, the entropy difference the sorption of gases both by organic polymers [17a] and by vitreous silica [17b].
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
ters, that is, log P0 versus EP , but in view of the better theoretical
basis for the entropy-adjusted form log Y0 , this first plot is not now
considered to be useful.
With certain exceptions [7], these three test plots were found
to be essentially linear, and may be fitted to the respective conven-
tional forms
Plot A : EP = m1 G + c1 (16)
Plot B : log Y0 = m2 G + c2 (17)
Plot C : log Y0 = m3 EP + c3 . (18)
In the context of the present paper, and to anticipate the
discussion on microporous silica in Section 3 below, these
plots are exemplified by Figs. 3–5, respectively, below (Section
3.4).
Before continuing with the interpretation of these Eqs. (16)–(18),
it should be emphasized that their linearity does not follow directly
from the theory, neither is it in any sense an integral part of it. It
should also be evident that these are not three independent equa-
tions, since they involve only three independent variables; this
leads to the parameters for the third equation as
m2
m3 = (19)
m1
(c2 m1 − c1 m2 )
c3 = . (20)
m1
As noted above, with the organic polymers not all the sys-
tems from the literature conformed to these linear relations of
Eqs. (16)–(18). In the case of the permeants G, the commonest
anomalies were seen [7] with the two permeants CO2 and H2 O.
The anomalies were in most cases only seen in the Plot A and
Plot C, and not in the Plot B (see Eqs. (16)–(18)), indicating that
this is related to an anomaly specifically in the permeation activa-
tion energy EP , with this value being lower than expected from
the behavior of other gases; this seems to be the cause of CO2
being a relatively “fast” gas in permeation [1,7]. At the time of
the previous publication [7] no clarification could be given of
this effect with CO2 . However, re-evaluation of this data [31]
indicates that there an essentially constant energy anomaly (low
EP ) of 18(5) kJ mol−1 for the organic polymers studied with this
permeant, with little if any correlation of the individual values
with such parameters as the cohesive energy density of the poly-
mer, or the enthalpy change of sorption HS of CO2 into the
bulk polymer. It seems that this effect results from to an ener-
getically favorable interaction between the quadrupole moment
of CO2 molecule at the transition site doorway and the polar
groups in the surrounding host matrix. This is thus an example
of the matrix-permeant energy contribution EMG towards EP in
Eq. (21). This interpretation is supported by the fact that CO2 is
well known to interact in a specific way with the bulk matrix of
many polymers [32,33]. This effect is also seen with silica (Sec-
tion 3 below) and is discussed further there. A similar energy
anomaly occurs with H2 O [7], where parallel interactions could
occur due to polar interactions, or possibly hydrogen bonding, at
the transition site doorway; this would also explain why H2 O is
also characterized as a “fast” gas (vapor) in membrane separation
processes [1].
2.7. Interpretation of the linear plots
The simplest explanation of these linear relations in Eqs.
(16)–(18) seems to be as follows.
In the first place, the linear relation of Eq. (16) (Plot A) indi-
cates that with increase in molecular diameter  G there is a parallel
47
increase in the internal energy change U‡ , shown to be equal to
the activation energy EP (Eq. (8)), to insert the molecule of G into
the doorway D (Fig. 1). Focusing on the expansion contribution Eex
in Eq. (14), if we follow this linear plot back down to its intersec-
tion point with the x-axis (EP = 0), this point then represents the
condition where there is no energy required, that is, the molecule
exactly fits into the doorway (see Fig. 3 below Section 3.4). This
indicates that for the set of permeant molecules considered, there
are a fixed number of pre-existing doorways of diameter  D that
control the migration of the permeant molecules through the host
medium. The energy dependence of Eq. (16) may then be put more
specifically in the form
EP = (G − D ) (21)
where the coefficient  is the force constant for the expansion of the
doorways for this host solid.
Likewise, the second linear relation Eq. (10) (Plot B) shows that
there is correspondingly a linear increase in the entropy of the
matrix at the doorway when the molecule is inserted, due to the
expansion by the inserted molecule (see Fig. 4 below Section 3.4);
this follows because log Y0 is directly related to the entropy change
[(S(GD) − S(D)] by Eq. (13), and the first two terms on the right hand
side of this equation are independent of  G . This may be put in the
more specific form:
(log e)(G − D )
log Y0 = log Yz + (22)
R
where the coefficient  is the corresponding entropy increment for
the doorway expansion process for that solid, and Yz is the limiting
value of Y0 for  G =  D .
These two parameters  and  therefore define the thermody-
namics of the expansion process. They are unusual in that, in the
case of the energy change, because this increases linearly with the
expansion, this represent a constant force being exerted by the door-
way, rather than an increasing force as might be expected for a
bulk solid with constant elastic modulus. In particular, it is in con-
trast with the form of Eq. (15) that is derived from the mechanics
of elasticity for a cylindrical cavity in the bulk solid; however, the
defects of this approach have already been noted in the discus-
sion of this equation. Speculatively, the linear behavior may arise
from the transition-site doorways being asymmetric (transversely
elliptical or slot-shaped) rather than being symmetric (circular) as
depicted by Fig. 1C.
This same Plot B also provides a method to obtain an estimate
of the doorway-spacing parameter , which equivalent to the jump
length of the diffusion model (Fig. 1). Considering Eq. (13) for log Y0 ,
the limit EP = 0 corresponds to  G =  D , with the gas molecule G just
fitting into the doorway, there will be no perturbation of the door-
way by the penetrant; so that not only will there be zero energy
change but there will also be zero entropy change, that is the
entropy term on the right of Eq. (13) will be zero; this corresponds
to the value of log Yz from Eq. (22). Thus Eq. (13) gives
k T 
B
log Yz = log − log  (23)
ehNA
from which in principle the value of  may be estimated since all
the other quantities in this equation are known.
Considering the third linear relation, Eq. (18) (Plot C), as already
noted its linear form follows directly from Eqs. (16) and (17) (see
Fig. 5 below Section 3.4).
The goodness of fit of these linear Eqs. (16) and (17) depends
necessarily on well-defined values of the molecular diameter  G ,
both with these organic polymers and with the inorganic amor-
phous solid, silica, considered in Section 3 of this paper. The sources
48 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
and suitability of these values are therefore discussed critically in
Appendix B.
2.8. Effects of finite uptake
As noted initially in Section 2.2, the present treatment applies
specifically to the “ideal case” of low pressures and low concen-
trations. In real systems there are often deviations at the higher
pressures and sorbed concentrations, so that the sorption coeffi-
cient S depends upon p, and D upon c.
In the TSM, these effects may be viewed in the first instance as
the result of the sorbed G on the characteristics of the doorways;
taking the spacing ␭ to be fixed for the material, this then involves
the remaining three parameters  D , , and . To disentangle these
effects, it would be necessary to measure EP and Y0 as before over
a range of uptakes c, with care being taken that the uptake is the
same for each range of temperature—for example, that there is the
same value of c at 25 ◦ C as there is at 200 ◦ C.
In some cases the sorbed molecules may be so strongly bound
as to have little if any effect on the transition-site doorways, so
that the value of P remains essentially constant. This seems to be
the situation in the case of H2 O with medium-polarity polymers
[7], and likewise of H2 O/oxidised PE [19] considered in Section 2.3.
This may also apply to the similar behavior for H2 with vitreous
SiO2 [18] also considered in that section.
At higher pressures there may be the purely hydrostatic effect
of the gas G upon the insertion process of Eq. (11), which may be
formalised as a volume change of activation V‡ ; this would lead
to a contribution pV‡ to the free energy change G‡ and thence to
the activation energy EP , which would thus show up in the Arrhe-
nius plots. At such higher pressures, it may be necessary to use the
gas fugacity as the activity-corrected form in place of the pressure.
At higher uptakes still there may be effects from blocking of the
sorption cavities to the release of the molecule from the TS doorway,
or plasticization of the whole solid matrix, but in this case the solid
must then be considered to be different in nature from the pure
material.
3. Application of the TSM to permeation through
microporous silica hollow-fiber membranes
3.1. Inorganic membranes for permeation
Although organic polymers continue to play an important role as
membranes for separation processes, there is an increasing interest
in inorganic membranes, because of favorable properties such as
greater heat stability [11,34]. It is therefore useful to see to what
extent the TSM model applies to this latter type of membrane. In
the present case, this is applied specifically to the inorganic glasses,
notably silica as the paradigm simplest case; some other types of
inorganic membranes are discussed briefly in Section 3.9.
There is a great bulk of previous literature studies on permeation
through and diffusion in glasses [3,5,6]. Unfortunately, it is difficult
to link these studies into a coherent picture, not least because there
are so many varieties of silica; for example, Doremus [35] has listed
four distinct commercial types of compact (nonporous) vitreous
silica. Furthermore, numerous novel types of microporous silica have
been developed recently, made for example, by the acid leaching
of borosilicate glass in hollow-fiber form [36–42], or as a sol–gel
form by coating a polymeric silica sol onto a more porous substrate
such as such as alumina [34,43–46]. In this context, “microporous”
implies a substance with pore diameter less than about 2 nm. Such
porosity is intended to confer a higher permeability than that for
the compact form, while at the same time retaining the activated
character of the migration so as to give useful separation of different
gases.
3.2. Permeation data of Way et al. for microporous silica
hollow-fiber membranes
In applying the TSM to microporous silica, what is required is a
set of data for a set of permeant gases having a range of molecular
diameters, studied over a sufficiently wide range of temperature
that good Arrhenius data may be obtained and the test plots of Eqs.
(16)–(18) may be applied as already discussed in Section 2.6. This
mirrors the requirements for the data sets for organic polymers
used in the previous development of the TSM [7]. This requirement
is largely fulfilled by the literature data on the microporous sil-
ica hollow-fiber membranes that were produced and patented by
PPG Industries [36,37], and that were used in the three permeation
studies published by Way and colleagues [38–40], where they were
referred to as “developmental products”. As detailed in the refer-
ences, the hollow-fiber membranes had been produced by melt
extrusion of a borosilicate glass, followed by exhaustive acid leach-
ing to remove Na and B, producing a network of pores with diameter
claimed to be less than 20 Å (2 nm) [36,37]. For the present pur-
poses, it is convenient to refer to this form of microporous silica as
␮SiO2 , to distinguish it from (for example) normal compact vitre-
ous silica, vSiO2 . However, this is only one example from a diverse
range of these materials.
Before considering these data further, it should be noted that
there are parallel data, on another sample of the PPG product, pub-
lished by Shelekhin et al. [41,42]. Since there are marked differences
in the results from these two groups, the latter are considered sep-
arately below in Section 3.8.
The fibers studied in two main papers from Way et al. [39,40] had
inside and outside diameters of the fibers of 35 and 45 ␮m, giving a
nominal wall thickness of 5 ␮m, while the material itself was found
to be amorphous, with about 20% porosity and with polydisperse
pores averaging about 10 nm. There was also physisorbed molecular
water (not quantitified) that was removed on heating above 450 K,
with exposure to the atmosphere at normal temperature leading to
its resorption.
The present paper focuses on the main studies in the two
later publications [39,40], which used nine permeant gases: Ar,
H2 , He, N2 , O2 , CO, CO2 , CH4 and C2 H4 , whose permeation rate
was measured over 25–200 ◦ C. A pressure differential p = 21.4 atm
(2.17 MPa) was used for the main permeation studies.
The studies also included measurements with gas mixtures;
such studies are naturally important in relation to gas separation
[1,11,41,45,47]. However, only the single-gas measurements have
been considered here.
For convenience of the future discussion, some important phys-
ical properties of these nine permeant gases are listed in Table 1:
(electrical) polarity factors (molar polarizability, dipole moment,
and quadrupole moment) [48,49], the absolute entropy S0 [50] (see
Appendix A), the critical constants [51], and various sets of values
of the molecular diameter  G [52–56] (see Appendix B).3
The data from first of the three Way publications [38] show
certain inconsistencies both internally (nonlinear Arrhenius plots)
and with the later data [39,40]; they must therefore be viewed
as only preliminary, and (except for He) they are not considered
further here.
3
Data in this paper are given in the internationally standard concise form: “mean
value (limits of error in the last decimal place of the mean value)”, so that for
example, “1.23(4)” represents “1.23 ± 0.04” (see: http://physics.nist.gov/cuu/ Con-
stants/index.htm).
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56 49

Table 1
Physical and molecular properties for the gases G that were studied as permeants with the microporous silica hollow-fiber membranes [38–40]

G Polarity factors S0 d Critical constantse Molecular diameters (pm)f

˛e a pe b Qe c pc Tc Vc Breck LJ CC

Ar 1.00 0 nd 251 4.87 151 75 340 343 (5) 295

H2 0.49 0 1.7 227 1.29 33 64 289 292 (4) 260
He 0.13 0 nd 222 0.23 5 57 260 258 (3) 210
N2 1.03 0 −4.7 288 3.39 126 90 364 371 (6) 313
O2 0.94 0 nd 256g 5.04 155 73 346 348 (8) 294
CO 1.18 0.4 −9.5 294 3.50 133 93 376 367 (7) 315
CO2 1.51 0 −14.3 310 7.38 304 94 330 398 (8) 324
CH4 1.47 0 nd 282 4.60 190 99 380 380 (6) 324
C2 H4 2.52 0 13.1 315 5.04 282 130 390 416 (7) 359
a
Molar electric polarisability (cm3 mol−1 ) [48,49].
b
Electric dipole moment (C m) × 1030 [49].
c
Electric quadrupole moment (C m2 ) × 1040 [49].
d
Absolute entropy at 298 K (J K−1 mol−1 ) [50], adjusted to 1 Pa as standard pressure—see Appendix A.
e
Critical constants: pressure pc (MPa), temperature Tc (K), molar volume Vc (cm3 mol−1 ) [51].
f
Molecular diameter values (pm) with sources: Breck [52], Lennard–Jones (LJ) [53–56], and “critical constants” (CC) [51]—see Appendix B.
g
Oxygen – special value of S0 – see Appendix A.

3.3. Permeability coefficients and the Arrhenius plots
Considering the two main papers, the data in earlier paper [39]
were reported as permeability coefficients P, whereas those in later
paper [40] were only quoted as permeances Q, that is, the ratio P/L
where L is the membrane thickness. Correlation of the two sets
of data indicated values of L between 4.4 and 4.9 ␮m; this is in
accord with the direct measurements for the internal and exter-
nal diameters [40] that gave L = 5 ␮m. The permeance values [40]
were accordingly converted into values of P using L calculated for
that sample. The Arrhenius plots for the combined data [39,40] are
shown in Fig. 2. The linear plots shown fit the experimental values
of P with an average deviation of 6%. The anomalous behavior of He
is considered below in Section 3.7 (see also Fig. 7).
3.4. Arrhenius data and derived parameters for the main gases
Table 2 lists the Arrhenius parameters for the eight gases (that
is, excepting He) derived from the linear plots in Fig. 2, together
with the values of log Y0 (entropic prefactor—Eq. (12)) derived using
the values of the absolute molar entropy S0 (at 298 K, adjusted to
the standard pressure 1 Pa) as given in Table 1. These Arrhenius
parameters may be taken to refer specifically to 298 K, since the
Arrhenius plots are linear at least down to this temperature (Fig. 2)
and the entropy values S0 do refer specifically to this value. Table 2
also show, for comparison, the corresponding literature values of
the Arrhenius parameters for permeation through normal vitreous
silica, vSiO2 ; only with four gases – Ar, H2 , N2 and O2 – are com-
parative data available for both types of silica [57], while there are
only from single literature sources for Ar [58] and for O2 [59]. The
comparison shows that the activation energies EP are much larger
with normal vitreous silica than they are with the present microp-
orous type. The EP -ratio for H2 is about 1.2, whereas those for the
other three gases the ratios are very similar, averaging 2.14(5); this
latter fact suggests that the structure of the present ␮SiO2 differs
in a consistent way from that of the normal compact form.
Reverting to the ␮SiO2 data, they are plotted along with the
molecular diameters  G to give the three plots as already used with
organic polymers [7] as discussed above (Section 2.4):

Fig. 3, Plot A: EP versus  G ;

Fig. 4, Plot B: log Y0 versus  G ;
Fig. 5, Plot C: log Y0 versus EP .

Table 2
Arrhenius parameters for the permeation of the gases G through microporous silica
(␮SiO2 ) hollow-fiber membranes (Fig. 3), derived in this paper from the data of Way
et al. [39,40], compared with literature data for compact vitreous silica (vSiO2 ) [57]

G ␮SiO2 vSiO2
9 + log P0 a EP b log Y0 c 15 + log P0 a EP b

Ar 0.87(4) 48.6(4) 4.98(5) 0.42d 106d

H2 0.38(5) 31.2(4) 3.18(5) 1.9(1) 37(1)
He nde nde nde 2.1(1) 22(1)
N2 0.12(13) 46.3(10) 6.11(13) 4.0(4) 100(8)
O2 0.64(6) 44.4(4) 5.01(6) 0.61f 93f
CO 0.70(5) 49.2(4) 7.06(5) nd nd
CO2 0.26(12) 38.9(10) 7.45(12) nd nd
CH4 0.89(10) 54.8(8) 6.62(10) nd nd
C2 H4 1.00(11) 57.8(8) 8.51(11) nd nd
a
P0 is the permeation prefactor (mol m m−2 s−1 Pa−1 ); note the different additive
factors for the ␮SiO2 and the vSiO2 results.
b
Permeation activation energy (kJ mol−1 ).
c
Y0 is the entropic prefactor (mol m m−2 s−1 )—see Eq. (12).
d
Fig. 2. Arrhenius plots for the permeation of gases as labeled through the micro- Single value [58].
e
porous silica hollow-fiber membranes. He: quadratic fit (but see also Fig. 6); other Nonlinear Arrhenius plot—see Figs. 2 and 7, and Section 3.7.
gases: best linear fits. Derived from the data of Way et al. [39,40]. f
Single value [59].
50 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
Fig. 3. Plot A—permeation activation energy EP versus molecular diameter  G for
gases through the PPG microporous silica hollow-fiber membranes. Key:  six gases
as labeled – the straight line is least-squares fit for this set; ♦ CO2 ;  CO2 – inter-
polated value, with the broken line indicating the energy anomaly EP ;  CO; 
He—extrapolated EP value. The extrapolation of the linear fit to EP = 0 gives the esti-
mate of the (unperturbed) doorway diameter  D as labeled. Derived from the data
of Way et al. [39,40].
The molecular diameters values  G used here are the “criti-
cal constant” values  CC listed in the last column of Table 1 (see
Appendix B), as previously used with the organic polymers [7]. In
each case the three plots are essentially linear, as previously seen
with the organic polymers [7]. The original papers [39,40] gave
similar plots to the present Plot A, using the Breck values [52] for
molecular diameter (see Table 1 and Appendix B), and also noted
the essential linearity.
Again, as with the organic polymers [7], deviations are seen with
CO2 , as discussed in Section 3.6 below; however, closer examina-
tion of the data indicated that the behavior of CO is also anomalous,
Fig. 4. Plot B—log Y0 (entropic prefactor) versus molecular diameter  G for permeant
gases with the PPG microporous silica hollow-fiber membranes. Key: ; six gases
as labeled – the straight line is least-squares fit for this set; ♦ CO2 ;  CO; : He –
extrapolated log Y0 . The extrapolation of the linear fit to EP = 0 is labeled with the
estimate of the (unperturbed) doorway diameter  D from Fig. 3. Derived from the
data of Way et al. [39,40].
Fig. 5. Plot C—log Y0 (entropic prefactor) versus permeation activation energy EP ,
for permeant gases with the PPG microporous silica hollow-fiber membranes. Key:
 six gases as labeled – the straight line is least-squares fit for this set; ♦ CO2 ;  CO;
: He – extrapolated (see Figs. 3 and 4). Derived from the data of Way et al. [39,40].
in that in the case of Plot B (Fig. 4) omitting this permeant as well as
CO2 gives a very good linear fit, with any deviations for the remain-
ing six permeants (H2 , Ar, O2 , N2 , CH4 and C2 H4 ) similar to those
suggested by the Arrhenius plots (Table 2). This indicates that, at
least with this set, the log Y0 values are well defined; this indicates
in turn that the EP values are also well defined, and that any devia-
tions in the Plot A (Fig. 3) and Plot C (Fig. 5) from linear correlations
represent systematic effects. The good linear fit in Plot B (Fig. 4)
also indicates that the  G values for these six permeants are well
defined, supporting the self-consistency of the “critical constant”
values  CC used here and derived as discussed in Appendix B.4.
It is therefore convenient to divide the interpretation of the
data into the primary effects, relating to the (average) straight lines
in the test plots, and the secondary effects, relating to systematic
deviations from these linear correlations.
3.5. Primary effects: H2 , Ar, O2 , N2 , CH4 , C2 H4
Considering the primary effects, the behavior of this group of
six gases relates mainly to the expansion of the SiO2 matrix, corre-
sponding to the energy contribution Eex of Eq. (14), the data from
the three linear Plots A–C results indicate, as discussed for the
organic polymers in Section 2.7, that the permeation of this set
of six gases involves a single fixed set of doorways with defined
diameter and defined spacing. The linear increase of EP and log Y0
results from the energy and entropy effects of inserting increas-
ingly large permeant molecules to expand the silica matrix at the
TS doorway (Fig. 1).4 Using Eqs. (21) and (22) gives the values of the
four characteristic parameters for the TS doorways listed in Table 3.
These values are similar to those seen with the organic poly-
mers [7], although in the latter case the thermodynamic parameters
in particular show a wide range of values because of the diver-
sity of polymers considered. As with the organic polymers, these
parameters must be considered average values.
It will be noted that these expansion effects are seen for perme-
ants ranging in size and molecular complexity from H2 up to C2 H4 ,
4
See footnote 2.
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56 51

Table 3 ically on the expansion contribution, Eex , as analyzed by Eqs. (21)

Parameters for the transition-site doorways in the permeation of gases through the
and (22). The secondary effects may be ascribed to the gas molecule
PPG samples of ␮SiO2 studied by Way et al. [39,40]a
in the transition-site doorway (Fig. 1C) interacting with the sur-
Name Symbol Value Units Figure Equation rounding silica matrix, presumably by polar interactions with the
Unperturbed diameter D 125(10) pm 3 (21) electrical distribution on the Si and O atoms of the matrix; this cor-
Force constant  0.43(7) nN 3 (21) responds to the contribution EMG of Eq. (14). Although no attempt
Entropy increment  1.7(2) pN K−1 4 (22) is made here to quantify these interactions, it is useful to note
Doorway spacing  30(4) nm 4 (22)
the degree of polarity for the various species involved. The com-
a
“Primary effect” data from the linear fits in the Figures specified for the six gases: mon factor here is the SiO2 matrix. There seems to have been little
Ar, H2 , N2 , O2 , CH4 , C2 H4 —see Section 3.5. mention on its charge distribution in discussions of its doorway
structure [20–25]; however, both Pauling electronegativity values
and including the intrinsically spherical (Ar) as well as the intrin- [60] and electron density measurements [61] give essentially +1.0
sically planar (C2 H4 ). This also shows the value of studying a wide unit charge on each Si atom and −0.5 unit charge on each O atom.
number and range of permeants, since it allows for a few to turn Carbon dioxide: The deviations with CO2 parallel those previ-
out to be markedly anomalous (here, He, CO and CO2 ) while still ously seen with organic polymers [7]; they correspond to the value
allowing sufficient remaining to define the main effects. of EP being lower than that expected by EP = 12 kJ mol−1 , but with
in this case also a marked entropy effect as shown by the apprecia-
3.6. Secondary effects ble (log Y0 ) value (Fig. 6). The effect seen so markedly with this
gas seems to be the result of the interaction of its large quadrupole
It is presumed in discussing these effects that the behavior all moment with the polar silica matrix as discussed; this quadrupole
the gases, including CO and CO2 as the most deviant cases, refers to moment has been modeled by a charge distribution with +0.66 unit
the same values of the average doorway spacing  and unperturbed charge on the C atom and −0.33 unit charge on each O atom [62].
doorway diameter  D that were estimated in the previous section Carbon monoxide: This gas is characterized by a marked
(Table 3). It is then convenient to quantify these secondary effects (log Y0 ) value (Fig. 6), essentially the same as that for CO2
in terms of the deviations in the two parameters EP and log Y0 from but a small if not zero value of EP . This anomaly also shows
the linear trends in Figs. 3 and 4, with the values of the respective itself in the Arrhenius plots (Fig. 2), where the plot for CO will
energy anomaly EP and entropy anomaly (log Y0 ) given by: clearly cross that for N2 at lower temperatures. The difference in
behavior of these two particular molecules is remarkable, since
EP = EP (cal) − EP (exp) (24) in their electronic structure and their critical constants they are
very similar and differ only in the presence of a small dipole
(log Y0 ) = (log Y0 )(cal) − (log Y0 )(exp) (25)
moment with CO (Table 1), which with the internuclear dis-
where “cal” indicates the value calculated from the trend Eqs. tance of 113 pm [49] corresponds to partial charges of only ±0.02
(21) and (22) for that value of  G , and “exp” indicates the exper- units on the respective atoms. Evidently the polarity of the SiO2
imental value (Table 2). These anomaly values are plotted against matrix again leads to a stronger effect than might have been
one another for display in Fig. 6. These effects may be discussed expected.
on the basis of the three contributions to EP shown in Eq. (14): Six gases: H2 , Ar, O2 , N2 , CH4 , C2 H4 . It will be seen from Fig. 6 that
EMM , Eex and EMG , but with the value of the first contribution these gases show appreciable and apparently significant values for
(matrix–matrix noncovalent interactions across the unoccupied the energy anomaly EP and with smaller and less significant val-
doorway) again neglected because of the width of the doorway ues of the entropy anomaly (log Y0 ). The values however seem to
(125 pm). The discussion of the “primary effects” focused specif- show no clear correlations with their molecular features (Table 1).
For example, C2 H4 has a similar quadrupole moment (albeit of the
opposite sign) to that of CO2 , but shows much lesser “secondary
effects” than the latter. Similarly, it is difficult to see why such three
different molecules as H2 , N2 and C2 H4 should be clustered together
(Fig. 6).
Summarizing, these secondary effects evidently arise because of
the much higher polarity of SiO2 than that of the organic polymers;
indeed, these effects may serve to probe the “fine structure” of the
TS doorways. However, although the deviations seen with CO2 are
understandable and parallel those seen with the organic polymers,
the picture for the other gases is much less clear. If the option exists
to extending these studies to other gases, the most useful would
be the other noble gases (Ne, Kr, Xe), since the simplicity of their
structure would greatly simplify the interpretation of the effects
observed.

3.7. Helium

As Fig. 2 shows, the Arrhenius test plot for He is markedly non-

Fig. 6. Entropy anomaly (log Y0 ) (Eq. (25)) versus energy anomaly EP , (Eq. (24))
for permeant gases with the PPG microporous silica hollow-fiber membranes. Key:
: six gases as labeled; ♦ CO2 ;  CO. Derived from the data of Way et al. [39,40].
linear (the curve drawn in the figure is an arbitrary quadratic best
fit). However, Fig. 7, which now includes the He data from the ear-
liest paper [38], shows that a simple plot of P (mol m m−2 s−1 Pa−1 )
versus T (K) gives an essentially linear dependence
1013 P = 0.030(T − 295). (26)
52 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
Fig. 7. Permeability coefficient P versus temperature for He and H2 through the PPG
microporous silica hollow-fiber membranes—data of Way et al. [38–40].  He, Ref.
[38]; ♦ He, Ref. [39]; +H2 [39,40]. The straight line is best fit to the He data; the curve
is the Arrhenius fit to the H2 data—compare with Fig. 2.
The same plot also shows the data for H2 as the next lightest gas,
with the best fit of the Arrhenius equation (Table 2).
This simple behavior of the temperature dependence of per-
meation for He does not seem to have been observed previously
in the literature, where for compact vSiO2 the dependence is
essentially Arrhenius even down to these low temperatures [57].
The parallel work of Shelekhin et al. [41] (see Section 3.8) also
gave an essentially linear Arrhenius plot for He with their sam-
ple of the PPG ␮SiO2 , while their EP values correspond to an EP
value of about 30 kJ mol−1 for the present Way sample (compare
with Figs. 3 and 5). If the He were escaping by Knudsen flow
through microscopic pores, the temperature dependence would be
as (1/T)1/2 .
At the same time, it is suspicious that the permeation flux
begins at a temperature (295 K) that is only a little below the
starting experimental temperature (298 K = 25 ◦ C), as if heating the
equipment were opening some apertures in the membrane sys-
tem through thermal expansion. However, the effect seems to
occur both with the data in first paper [38] and those in the third
paper [40], where different samples of the hollow-fiber membrane
were used (Fig. 6). It is also curious that with rise in temper-
ature the permeation rate for H2 eventually overtakes that of
He (Figs. 2 and 6); any anomalous permeation mechanism for
He would be expected to be additional to the normal Arrhe-
nius rate, which should be should be markedly higher than that
of H2 .
This simple but curious behavior of He therefore remains unex-
plained.
3.8. Permeation data of Shelekhin et al. on the PPG microporous
silica hollow-fiber membranes
It has already been noted, in Section 3.2, that parallel permeation
studies on the PPG microporous silica hollow-fiber membranes
have also been carried out by Shelekhin et al. [41,42]. Although
these data, and those of Way et al. [38–40], already considered
in some detail, were obtained on what was nominally the same
type of type of PPG product [36,37], it is evident that there were
marked differences between the two materials used. The Shelekhin
fiber sample, for example, had a smaller outside diameter (32 ␮m)
and inside diameter (22 ␮m), although with the same nominal wall
thickness (L = 5 ␮m). Five gases were studied with this sample: He,
H2 , O2 , N2 , CH4 , CO2 ; the permeation of these was studied over
the temperature range 30–250 ◦ C, except for H2 that was studied
at only 30 ◦ C. Both sets of Arrhenius parameters were lower than
those for the Way samples (Table 2); the Shelekhin sample values
of log P0 were 3.9 units lower for O2 and N2 , and 4.6 units lower
for CH4 and CO2 ; for EP there were a fairly consistent lowering of
33(2) kJ mol−1 for all four of these gases. The lower values of EP
seem to be an extension of the reductions seen in going from the
compact vitreous silica vSiO2 to the microporous silica studied by
Way et al. (Table 2).
Their data were interpreted by the authors [42] on the basis of
the SDM. However, using the present TSM, the EP values gave a
rather scattered linear Type A plot (not shown) for the four gases:
He, O2 , N2 , and CH4 , where the downwards shift in EP corresponds
to a higher value of the doorway diameter  D = 240(20) pm (com-
pare with Fig. 4); the EP value for CO2 was again low, in this case by
about 11 kJ mol−1 .
It seems that the larger doorway size with the Shelekhin sample
compared the Way sample is the result of differences in the produc-
tion histories of these samples. Comparative results of this kind on
suitably diverse sets of permeant molecules with membrane sam-
ples prepared under different controlled conditions promise to give
some clues as to the factors influencing the four TSM parameters
( D , , , ) that determine permeation behavior.
3.9. Other microporous inorganic media
The microporous silica discussed in Section 4 is only one type
in a wide range of such media whose gas permeability behav-
ior is important in practice [1,11,14,34,52]. Two other important
types are the zeolites, with their open-network crystalline struc-
ture, and where the crystallographically defined windows are the
equivalent of the present doorways [1,9,11,12,14,52], and the micro-
porous carbon membranes, also referred to as carbon molecular
sieve membranes (CMSM) [11,13,34,47].
With these materials, insofar as the pore size and the perme-
ant molecular diameter lead to activated migration and molecular
sieving, the TSM should again be applicable. As with the organic
polymers [7] and the present microporous silica (Table 1), this again
requires experimental permeation data over a wide temperature
range with a set of permeants having a spectrum of molecular diam-
eters to probe the doorways and define their characteristics; the use
of nine permeants in the present case seems exemplary. Once again
the TSM obviates the need, inherent with the SDM in experimental
and in modelling studies, to deal separately with the sorption and
the diffusion processes.
4. Conclusions
• In this paper, the previously presented transition-site model
(TSM) as applied to organic polymers has been re-presented
briefly with some changes in detail.
• The conventional and widely accepted sorption-diffusion model
(SDM) used to describe permeation through solids has now been
reviewed critically; one key feature of the present paper is the
observation that there is a fundamental point of weakness of the
SDM, in that the two analyzed factors, “sorption” and “diffusion”,
are not independent, since both contain the characteristics of the
sorption state. Other points noted are that the sorption sites must
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
be heterogeneous in character, and that the pressure differential
and not the concentration gradient is the true driving force for
the migration.
• By contrast, the strength of the TSM lies in its focus on the
transition-sites that it turns out are already accepted as doorways
for migration in nonporous inorganic glasses such as vitreous
silica.
• The TSM allows analysis of the linear test plots to estimate the
four characteristic quantities: the intrinsic diameter of the door-
way,  D ; the thermodynamic parameters for the expansion of
the doorway,  (force constant) and  (entropy increment); and
the average spacing between neighboring doorways , which is
equivalent to the “jump distance” of the SDM.
• The TSM has the advantage over the SDM that if decouples the
migration process from the sorption equilibrium. Strictly, this
only applies in the limit of low pressures and low amounts of
sorption; the actual amount of sorption only comes in as a per-
turbation effect, that is, of the sorbed molecules on the properties
and behavior of the doorways.
• The present work has shown that the TSM applies to one particu-
lar type of microporous silica hollow-fiber membrane produced
by PPG Industries, and that it gives values for the four character-
istic parameters that are similar to those obtained with organic
polymers. There are also some “secondary effects” that are inter-
preted as host-guest interactions at the doorway.
• These results suggest that the TSM should be applicable more
widely to inorganic membranes showing activated permeation
by molecular sieving, including other types of microporous solids
as well as zeolites and other crystalline solids.
Appendix A. Absolute molar entropy values, S0
The values of the absolute molar entropy, S0 , for the gases play an
important part in the TSM, in correcting for their different entropy
levels in the gas state on either side of the membrane, and putting
these on the same basis as the energy values which are all on the
same (zero) level in the gas state. There are two points to be noted
in connection with these values listed in Table 1.
The first point relates to the matter of the pressure units that
are used as the reference level in defining S0 , since this must be the
same as the pressure units used for the permeability coefficient;
this reference level relates to the entropy change that takes place
when the solid (crystalline) form of the substance (with entropy
essentially independent of pressure) is converted to the gas (vapor)
state. In a previous publication [63] this reference level has been
considered as a form of “hidden” unit; an alternative method would
be to simply use permeability coefficients that are referred to the
same standard pressure unit of the absolute entropy value, although
this is not such a transparent way of working. In either case, the con-
version from the literature values of S0 [50] with the bar (=105 Pa)
as the standard state pressure, to the pressure unit Pa used in the
permeability coefficient, requires the addition of R ln(105 ), that is,
96 J K−1 mol−1 ; the values so adjusted are listed in Table 1, and used
in the calculation of the entropic prefactor Y0 using Eq. (12).
The second point relates specifically to the value of S0 to be used
for O2 . In the case of the organic polymers [7], it was found that
using the value of 301 J K−1 mol−1 obtained by applying the above
pressure-unit adjustment, with all the polymers where O2 had been
studied alongside a number of other permeant gases, in each case
it gave the same anomaly with the Plot B and the Plot C, but no
anomaly with the Plot A; this indicates that the anomaly relates
to a high value of the parameter log Y0 (entropic prefactor). Since
this occurred in a consistent way with all of the polymers involved,
and unless the anomaly relates to a different value of the rate coeffi-
53
cient or lattice parameter for this gas – Eqs. (16)–(18) – then the only
common factor is the gas itself. This was therefore dealt with prag-
matically by using the lower value of 256 J K−1 mol−1 for this gas,
which removed the anomaly for this gas in all the cases involved.
This has also been done in the present case (Table 1), and leads to
a good fit in the Plot B (Fig. 4) and Plot C (Fig. 5), as well as in Plot A
(Fig. 3) where this factor is not involved.
Appendix B. Molecular diameters of permeant gas
molecules,  G
B.1. Importance of molecular diameter values
In the evaluation and interpretation of the migration of guest
molecules in solids from the molecular viewpoint, it is evidently
necessary to have a self-consistent set of molecular diameters for
the gases used; however, there seems to have been little specific
or critical examination of these diameter values used in this area
[2,3,7]. This requirement is particularly important for the accu-
rate estimation of the diameter of the unperturbed doorway  D ,
of the thermodynamic parameters  and  for the expansion of the
transition-site doorway, and of the inter-site spacing . For each of
these depends on the good linear definition of the three test plots
(see Figs. 3–5).
In quoting these values, it is found clearer to use picometers
(1 pm = 0.01 Å = 0.001 nm) since these shows up better the effect of
small changes on the permeation behavior.
There are three main sets of values that have been applied in
the area of permeation through membranes, as considered below
in Sections B.3 and B.4. However, it is necessary firstly to consider
the effect of rotation on the effective molecular diameter.
B.2. Rotation of molecules in relation to molecular diameters
In considering the specific dimensions of molecules, and in
particular how they pack together in the solid-state at low tem-
peratures, it is evidently necessary to consider the detailed shapes.
Commonly, this can be summarized as spherical, rod-shaped, pla-
nar, etc. Frequently, in considering the migration properties of
molecules in solids, these shapes are referred to in order to clar-
ify or interpret the behavior; for example, a rod-shaped molecule
is commonly presumed to present its narrowest dimension to the
barrier to ease its passage. However, this ignores the significance of
rotation in the behavior of the molecule. At a high enough tem-
perature, a molecule will have an amount kB T/2 in each axis of
rotation; in macroscopic terms, this energy amounts at 25 ◦ C to
about 1 kJ mol−1 . Although rotation is suppressed for all molecules
at sufficiently low temperatures, as the temperature is raised quan-
tum effects lead to the onset of rotation. This is shown by the values
of the heat capacity at constant pressure Cp , which in the general
case rises with temperature as firstly translation, then rotation and
then vibration modes come into play [64]; the literature data for Cp
show that this rotational freedom is essentially complete at 298 K
for all the molecules considered here [65]. The angular velocity ω
will be given by the standard mechanics formula relating it to the
moment of inertia I of the molecule about that axis
kB T Iω2
= . (B.1)
2 2
For molecules of the type used here as permeants
(Tables 1 and 2), this gives angular velocities ω in the range
of 1012 to 1013 s−1 [64]. Thus if a specific orientation is envisaged
for the permeant molecule in the doorway, this very rapid rotation
must be stopped. At the same time, the orientation involves an
entropy penalty, related to the degree of restriction envisaged,
54 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56
since there must still some finite degree of motion (oscillation)
in the captured state. For example, an allowed oscillation of ±10◦
about the long axis in all directions reduces the directional freedom
by a factor of about 100, that is, only about 1% of the molecules
would be oriented in this way ready for insertion; from the
thermodynamic viewpoint, this would correspond to an entropy
penalty S of about 40 J K mol−1 , leading at 298 K to an free energy
penalty (TS) of about 12 kJ mol−1 . More stringent limitations on
the freedom on the molecule lead to a correspondingly smaller
fraction of molecules with the correct orientation, and paralleled
by correspondingly greater thermodynamic penalties; the latter
would also be greater still at higher temperatures. These consider-
ations strongly suggest that, in the first instance, molecules of all
kind should be considered as rotating essentially freely, that is, to
be spherically symmetrical, both in the gaseous state and when
inserted in the transition-site doorway, and that it is the diameter
of this sphere of rotation that determines the effective molecular
diameter.
B.3. Molecular diameter values of Breck
One widely used approach in permeation work is to use the set
of values listed by Breck [52] in connection with zeolite molecular
sieves, which has been also adopted for use in the field of membrane
processes in general [1], and more specifically in the publications
drawn upon in this paper [38–40]; indeed, these values seem to be
viewed as definitive. The original values [52] were drawn from a
diversity of sources, including Lennard–Jones parameters (Section
B.4) in a rather inconsistent fashion; being put in Angstrom (Å)
units, it is not clear what precision is being claimed: “3.9 Å” may
imply either ±1 or ±5 on the derived value of 390 pm.
In addition, in the cases of the isoelectronic pair, CO2 and N2 O,
the values have been taken to be those of the smallest diame-
ter, leading to quoted values of 0.33 Å, that is 330 pm, giving the
anomaly that they have a lower value than that for patently smaller
molecules such as CO, N2 and O2 ; this anomalous value has appar-
ently been accepted by the membrane community because it fits
in with this being a “fast” gas in permeation, although the present
treatment has shown that this is an energy effect (low EP ) rather
than a molecular diameter effect. Further evidence on this point
is given by the electric polarisability ˛e , which is another mea-
sure of molecular volume; the value for CO2 is some 50% greater
than those for these same diatomic molecules (Table 1). Indeed, as
already noted (Section B.2), all these molecules must be taken to
be rotating freely in the gas state, and would tend to maintain this
rotation even when held in the guest matrix, so that the diameter to
be assigned to these triatomic molecules is the largest dimension.
Furthermore, it is not clear whether or not this “adjustment” for
CO2 and N2 O has also been applied to other asymmetric molecules
(C2 H4 , C6 H6 , etc.).
A similar anomaly is evident for the pair: H2 (289 pm) versus
H2 O (265 pm) [52]. This anomaly is again highlighted by the fact
that the volume-related molar polarizability ˛ of H2 O is nearly
twice that of H2 [48], whereas the converse situation should occur
if the quoted Breck values apply.
It is also not clear whether this set of parameters, which has
been selected specifically to apply to the zeolites, is necessarily
going to apply to such diverse other media as (for example) organic
polymers, silica, and microporous carbon.
B.4. Lennard–Jones diameters
An alternative approach is to use the parameters derived from
the Lennard–Jones (LJ) 6–12 potential for the intermolecular poten-
tial energy u(r) of a pair of identical molecules at internuclear
separation r
 12   6
LJ LJ
u(r) = 4 εLJ − (B.2)
r r
where εLJ is the depth of the potential well and  LJ is the LJ
molecular diameter [2]. More exactly, this equation only applies to
nonpolar molecules (especially the noble gases); with polar gases
there would be a third term for the polar (electrostatic) contribu-
tions, leading to the so-called Stockmayer equation. Table 1 shows
the values of the LJ diameters from the literature [53–56]. The
values originate from one of three sources of experimental data:
gas viscosity, thermal conductivity, or equation of state (second
virial coefficient). The problem with all these methods is that they
may only give a combination of the two parameters εLJ and  LJ .
This shows itself, when considering LJ parameters from different
sources, in a “high” value of εLJ being associated with a “low” value
of  LJ , and vice versa. The data given in Table 1 have been evalu-
ated in the light of these considerations, eliminating some values
that were evidently anomalous. Even with this procedure, as shown
in Table 1 the uncertainty in these values is still about 6 pm. In
addition, any polarity of the molecules makes the application of
the simple form of Eq. (B.2) less certain. In the case of CO2 in par-
ticular, there are indications that the LJ parameters are markedly
temperature dependent [53]. There is also the general limitation
that these parameters require the availability of experimental data
from one of the three rather troublesome experimental methods
already specified.
B.5. Molecular diameters from critical constants via the van der
Waals equation
A third approach is to use parameters derived from the co-
volume b of the van der Waals equation, as in the previous paper [7].
The rationale here is that the parameter b is presumed to be equal
to four times the volume of the molecules, leading to the relation:
 3b 1/3
= . (B.3)
2NA
With values of b available from the literature [66], this enables 
to be determined for these same molecules. However, appearances
are deceptive since it turns out that the listed values of b [66] are
not from a van der Waals fit, but are derived from critical constants
using the relation
RTc
b= (B.4)
8pc
where Tc is the critical temperature and pc is the critical pressure;
it is somewhat odd that it is not the critical molar volume Vc that
is used, but presumably the logic is that the value of Vc is in many
cases either lacking or not well defined in the literature [51]. How-
ever, this has the advantage that the critical constants Tc and pc are
known for a very wide range of substances [51], while unlike the LJ
values (Section B.3) there are no ambiguities from any polarity of
the molecules. This leads finally to:
 3RT 1/3
c
CC = (B.5)
16NA pc
where the subscript on  CC is used to indicate specifically the source
of the values. Judging from the data for the present substances
(Table 1) supplemented by that for the other noble gases, these  CC
values are fairly consistently 15% less the corresponding  LJ values.
Some ambiguities arise here with the “light” gases, notably He
and H2 (and their isotopes) and to a much lesser extent Ne, where
quantal (quantum mechanical) effects come into play. In the case
 P. Molyneux / Journal of Membrane Science 320 (2008) 42–56 55

of the noble gases (He, Ne, Ar, Kr, Xe), this is evidently cause of
the anomaly, that Ne has a smaller derived value of  CC than He,
S‡ molar entropy change for insertion of G into a TS
although the values thereafter increase smoothly for Ne–Xe. How-
doorway (J K−1 mol−1 )
ever, these directly calculated values were found to be satisfactory
T absolute temperature (K)
in the previous application of the TSM model to organic polymers
Tc critical temperature (K)
[7], while quantal effects are themselves present in the perme-
TS transition-site (doorway)
ation of gases through amorphous media, for example with organic
TSM transition-site model for permeation
polymers [10]. In the present case the  CC values for He and H2
U‡ molar internal energy change for insertion of G into
given in Table 1 have been adjusted by using the linear relation
a TS doorway (J mol−1 )
that is observed between  CC and ˛1/3 , where ␣ is the volume-
Vc critical molar volume (m3 mol−1 )
dimensioned molar polarizability as also listed in Table 1.
x general membrane depth in the direction of perme-
In the present work with microporous silica, it is these  CC val-
ation (m)
ues, as listed in the last column of Table 1, that have been used as
Y entropic coefficient Eq. (18) (mol m m−2 s−1 )
the molecular diameter  G in the test plots of Figs. 3 and 4, and in
Y0 entropic prefactor Eq. (19) (mol m m−2 s−1 )
the calculation of the derived parameters for the doorways listed
(log Y0 ) entropy anomaly (Eq. (25))
in Table 3.
 times-or-divided-by

Greek letters
˛e molar electric polarisability (m3 mol−1 )
Nomenclature εLJ Lennard–Jones energy parameter (J)
 force constant for expansion of a TS doorway (N)
b van der Waals co-volume (m3 mol−1 )
 (average) spacing between neighboring TS door-
D diffusion coefficient (m2 s−1 )
ways (m)
D location of a doorway (transition-site)
 entropy-change coefficient for expansion of a TS
D0 diffusion prefactor (m2 s−1 )
doorway (N K−1 )
Eex energy to expand the TS doorway by the inserted G
 molecular (kinetic, collision) diameter (m)
molecule (J mol−1 )
D diameter of an unoccupied TS doorway (m)
ED activation energy for diffusion (J mol−1 )
G molecular diameter of the permeant gas G (m)
EP activation energy for permeation (J mol−1 )
 CC value of  estimated from critical constants
EMG energy of noncovalent interaction between the
(Appendix B) (m)
inserted G molecule and the TS doorway matrix
 LJ Lennard–Jones molecular diameter (Appendix B)
(J mol−1 )
(m)
EMM energy of noncovalent interactions across the unoc-
cupied TS doorway (J mol−1 )
EP energy anomaly Eq. (24) (kJ mol−1 )
G bulk shear modulus (Pa) References
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