The Effect of Pore Space Connectivity on the Hysteresis of Capillary

Condensation in Adsorption-Desorption Isotherms

GEOFFREY MASON
Department of Chemical Engineering, Loughborough University of Technology,
Loughborough, Leicestershire, England
Received April 13, 1981; accepted October 16, 1981

A method of determining the connectivity of the pore space of an adsorbent from the hysteresis
of the adsorption-desorption isotherm is proposed. The analysis depends upon being able to theo-
retically separate the a m o u n t adsorbed into capillary condensation and surface adsorption and uses
the a m o u n t of capillary condensation on the adsorption isotherm at the relative vapor pressure of
the desorption knee as the variable determining connectivity. As an example the analysis is applied
to known isotherms for Linde silica.

INTRODUCTION liquid, termed capillary condensation, con-

Adsorption-desorption isotherms of gases
on materials with large surface areas take
many forms. Often they are reversible but
in many cases the experimental adsorption-
desorption isotherms exhibit hysteresis. There
are several theories and explanations of this
hysteresis and it is the purpose of this paper
to expand one of them, namely, that under
certain circumstances, hysteresis can be
mainly produced by pore space interconnec-
tivity.
A D S O R P T I O N O F G A S E S BY P O R O U S S O L I D S
Adsorption data are usually reported as
an amount adsorbed per unit weight of ad-
sorbent at a particular relative vapor pres-
sure. As the relative vapor pressure is in-
creased one visualizes increasing amounts of
adsorbate becoming attached to the surface
of the adsorbent. At some stage a monolayer
is completed and further adsorption results
in a multilayer being formed. This multi-
layer begins to behave like normal liquid and
may become unstable and flow to new con-
figurations (1) and fill pores. Depending on
the existence of pores and the structure of
the pore space this increasing quantity of
36
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tinues to build up until, at a value of relative
vapor pressure less than unity, all of the pore
space is filled.
The size and shape of the pores clearly
have a large effect on this behavior. If a po-
rous material is composed of an assembly of
rotund particles then as the multilayer be-
gins to form, pendular rings of liquid are
produced at the points of contact between
the particles (2). If, however, the porous
material is formed by a foaming process then
in essence it is an assembly of rotund voids
and will exhibit no such pendular ring for-
mation.
An important part of the mechanism of
adsorption in large assemblies of pores is
that all of the pores are in contact with Vapor
at all times. Only in exceptional circum-
stances are parts of the surface obscured and
blocked to the adsorbing vapor molecules.
DESORPTION OF GASES FROM POROUS
SOLIDS
When the relative vapor pressure reaches
unity all of the pore space is completely filled
with capillary condensed liquid (or solid if
the temperature is sufficiently low). If the
relative pressure is reduced then this liquid
Journal of Colloidand lnterfaceScience,Vol. 88, No. 1, July 1982
 EFFECT OF PORE SPACE CONNECTIVITY
begins to desorb. Now, depending on the
structure of the pore space, different things
can happen. If the pore space consists of a
relatively coarse network of large pores with
smaller pores attached then the coarse net-
work empties giving access to all the smaller
pores and these can empty in turn. In this
case most of the pores have some direct con-
tact with the vapor and s o we have similar
conditions to adsorption but in reverse. If
such a system exhibits hysteresis then a suit-
able explanation of this hysteresis is given
by the classic ink-bottle pore (or other pore
configuration such as assemblies of plates)
where the individual pore characteristics are
different for adsorption and desorption (3).
If the pore space consists of large and
small pores mixed together and highly in-
terconnected such as the pore space of a
packing of rotund particles, then as the rel-
ative vapor pressure is progressively reduced
and as liquid desorbs, the liquid menisci in
the outer pores develop a curvature to main-
tain equilibrium with the vapor. This cur-
vature of the menisci develops a negative
tension in the liquid which, if sufficient, may
cause the liquid column to rupture and de-
sorb a large amount of vapor (4). Alterna-
tively some of the outer surface of the porous
material where the pores have access to the
vapor may empty. The interconnections from
this partially emptied region may not be suf-
ficiently numerous in relation to the pores
which have emptied to give general access
of the pores to the vapor. If the relative pres-
sure is reduced further then the equivalent
of a chain reaction occurs with a sufficient
fraction of every new group of pores emp-
tying to give access to even more pores. This
process gives a very steep portion on the de-
sorption isotherm and the system will exhibit
hysteresis as a result of this desorption mech-
anism in addition to any hysteresis caused
by the properties of individual pores.
ADSORPTION-DESORPTION HYSTERESIS
The theoretical explanation of hysteresis
in the capillary condensed liquid portion of
37
the isotherm is complicated by the fact that
variable amounts can be adsorbed at a par-
ticular value of the relative pressure de-
pending on the past history of the isotherm.
Various explanations of the hysteresis have
been advanced (see (5)) including hysteresis
of the liquid-solid contact angle, the exis-
tence of ink-bottle pores, the detailed mech-
anism of condensation on the walls of the
pores and their evaporation, the effect of
multilayers, and finally pore space connec-
tivity. The theory of each of these mecha-
nisms has been derived with Varying degrees
of plausibility but most seem less plausible
or too difficult to apply when pressed to ex-
plain the scanning curves inside the adsorp-
tion-desorption hysteresis loop. One of the
more successful is Everett's independent do-
main theory (6) approach to ink-bottle pores
in suggesting a distribution of pores of dif-
ferent sizes each with their own different in-
built ink-bottle pore hysteresis.
An important problem in explaining the
capillary condensation hysteresis is the sep-
aration of the amount of adsorbed gas into
particular types depending on the relative
pressure so that the relevant theory can be
applied. For relative pressures in the range
0-0.3, where there is no capillary conden-
sation the BET (7) theory and equation is
considered to give a good account of both
adsorption and desorption. Above a relative
pressure of 0.3 where pendular rings may be
formed between particles (if the adsorbent
is made of particles) the analysis made by
Wade (4) is more appropriate. In the region
of capillary condensation where the relative
pressure is between 0.5 and 1.0 the appli-
cation of the Kelvin equation (8) to a par-
ticular pore geometry such as a tube or a
spherical void is often sensible. We thus have
separate theories for different values of rel-
ative pressure but, adsorption being what it
is, these theories are really being applied to
an increasing thickness of adsorbed mole-
cules, each upon the molecules beneath, and
it becomes difficult to separate them quan-
titatively into the range covered by the rel-
Journal o f Colloid and Interface Science, Vol. 88, No. 1, July 1982
38
evant theory. In the application of the fol-
lowing model it is assumed that one could
determine the amounts of capillary con-
densed liquid and multilayer adsorption, the
two summing together to give the total
amount adsorbed.
CAPILLARYCONDENSATION IN A MODEL
PORE SPACE
Capillary condensation in a pore space in-
volves both filling with condensed liqu!d,
during adsorption, and emptying during de-
sorption. Adsorption is a function of pore
size alone but desorption is a function of both
pore size and connectivity. Any theory will
depend critically on the particular model
chosen for the pore space with regard to both
pore size and interconnectivity.
The model proposed here envisages an in-
dividual pore to be a cavity in the solid ma-
trix connected by windows to adjacent cav-
ities. The number of windows per cavity will
be termed the connectivity (c) and will be
taken to be a constant for any particular
porous material.
A value for the adsorption meniscus radius
associated with each cavity can be deter-
mined from the relative pressure at which
it fills by the Kelvin equation
-2~V'cos ~b
r-
R T In (P/Po)'
where cr is the liquid surface tension, V' is
the molar volume of the liquid adsorbate,
is the liquid-solid contact angle (usually
assumed to be zero), R the gas constant per
mole, T the absolute temperature, and P/Po
the relative vapor pressure. This gives the
radius, r, of the liquid meniscus at which the
single cavity fills with liquid. If the number
density function of all cavity radii is g(r)
then g(r)dr represents the probability of a
random single cavity having an adsorption
meniscus radius between r and r + dr.
Each cavity has c windows which must,
from geometrical considerations, have as-
sociated radii smaller than the adsorption
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
GEOFFREY MASON
meniscus radius. There will be a desorption
meniscus radius associated with each win-
dow (also related to P/Po by the Kelvin
equation) and if the density distribution of
these window radii is f(r) then the proba-
bility of a random window having a desorp-
tion meniscus radius between r and r + dr
is f(r)dr. This assumes that the window radii
associated with each cavity are independent
and not correlated.
RELATION BETWEEN ADSORPTION AND
DESORPTION PORE RADII
The functions f(r) and g(r) can be re-
garded as exact definitions of what is loosely
termed the pore size distribution. They, to-
gether with the connectivity factor, c, are
taken to define the pore space of any porous
material. But so many data are required to
determine f(r) and g(r) that, although they
are theoretically interesting, they are in
practical terms useless. However, f(r) and
g(r) are related because for any individual
cavity the largest desorption window radius
(one of c) must, from geometrical consid-
erations, be less than the single adsorption
radius. This gives each cavity, when treated
as an isolated system, a degree of hysteresis
in that the value of P/Po at which it fills will
be greater than the value of P/Po at which
it empties. Everett's domain theory (6) relies
on this individual pore hysteresis alone, with-
out any connectivity effects, to explain the
hysteresis of the total system. But what if
connectivity effects are dominant and there
is no hysteresis exhibited by an individual
isolated pore? Then the largest desorption
window radius is the same as the adsorption
radius and, for this special case, the relation
between f(r) and g(r) can be quantified.
Consider a value of the desorption window
radius, rp, related by the Kelvin equation to
the relative vapor pressure. The probability,
p, of a window having a radius less than rp
will be given by
p = f(r)dr. [ 1]
 EFFECT OF PORE SPACE CONNECTIVITY 39

19.025
If we define a parameter q as the fraction
of cavities filled at some adsorption window
radius rq (the adsorption equivalent of p)
then

q = L rq g(r)dr [3]

0 and integration of [2] gives

0.'2 014 0'.6 R
r q =pC. [4]

It is possible to test the likelihood of no hys-

teresis being exhibited by an individual iso-
lated pore for the special case of a pore sys-
tem formed in a random packing of equal
spheres. Mason (9) modeled the pore space
of a random packing of equal spheres as an
0.2 0.4 0,6 R assembly of tetrahedral subunits and cal-
r
culated the window radii and cavity insphere
radii for 1000 individual tetrahedral pores.
The distributions of f,(r) and gs(r), the ap-
propriate radius distributions for the pores
in a sphere packing, are thus approximately
known. Using Eq. [2], gs,t(r), the theoretical
distribution, was calculated from fs(r) using
a step size of 0.01R, where R is the radius
of the packed spheres, fs(r) is more precisely
n known than g,(r) as 4000 window radii were
0
0 0.2 0.3 O,6R used by Mason (9) to compute f~(r) but only
r
1000 cavity insphere radii were used to com-
FIG. 1. The window radius distribution, f,(r), and the pile g,(r). As the calculation involves using
cavity radius distribution, g,(r), for tetrahedral pores in
histogram data with step changes in dr as
a sphere packing as given by Mason (9) and the theo-
retical cavity radius distribution, gs, t(r), derived from opposed to the ideal continuous distribution
fs(r) using the assumption that there is no hysteresis in of the theory a problem arises in the value
an individual isolated pore. The distributions g~(r) and of rp used to calculate p and actually g(r)s,t
g,.t(r) show broad general agreement except for the was calculated from
smaller radii. Radii are expressed in terms of the sphere
radius of the spheres making up the packing. g~.,(r)Ar

So the probability of an individual cavity =hJo

having any one window between G and rp
+ drp and also the remaining (c - 1) win-
dows smaller than rp will be
cpc-lf(rp)drp .
But if there is no individual pore hysteresis
then this is the adsorption radius distribution
SO
g(rp)drp : cp c-1/(rp)drp.
r rr*Ar
fs(r)drJ -
]4 ILr
f,(r)dr
]4 [5]
although the difference between this method
and assuming that half of the windows in
any one histogram column are smaller than
the mean is negligible except for the first
column of the distribution (i.e., the smallest
windows). Figure 1 shows f,(r) and g~(r), the
distributions given by Mason (9), and gs,t(r)
[2] which was calculated as explained above
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
40
from f~(r) on the basis that there was no
individual pore hysteresis. The distributions
gs(r) and gs.t(r) agree quite well except for
small values of r. The disagreement here is
to be expected as there are a number of reg-
ular tetrahedra in Mason's model and these
give the smallest window radii (0.1547R)
and also the smallest cavity radii (0.2247R).
As these two are different the two distri-
butions will cut off at different points for the
smallest radii. Apart from the smallest radii
then, surprisingly, the assumption that there
is little hysteresis attributable to the prop-
erties of individual pores seems reasonable
for the pore space of a random packing of
equal spheres, the only system for which
there are data. Most of the hysteresis exhib-
ited by such a system must come from the
connectivity of the pore space.
PORE VOLUME AND PORE RADII
The functions g(r) and f(r) are number
distributions of pore radii. A real isotherm
of adsorption and desorption is dependent
not only upon numbers but the volumes as-
sociated with each radius. To relate the as-
sociated volume distribution at a particular
radius to the number distribution it is com-
mon to assume that the larger the pore ra-
dius the larger the associated volume (10)
and to assume some functional relationship
between them (i.e., a cubic). The volume
distribution for Mason's tetrahedral pores
shows that some tetrahedron volumes are
less than the volume of the regular tetra-
hedron. An increase in the length of the
edges of a tetrahedron does not always in-
crease its internal volume as, depending on
which edges of the tetrahedron are extended,
it can lose height. In fact, the ultimate is for
the tetrahedron's six edges to be reduced to
a square and its two diagonals; the tetra-
hedron volume is then zero. So for the pore
space of a random packing of spheres there
may be a correlation between pore radii and
cavity volumes but it is not very strong and
the alternative assumption, that a cavity VO1-
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
GEOFFREY MASON
ume is independent of the window radii and
cavity filling radius, seems just as attractive.
More so, as the analysis is correspondingly
simplified.
The two assumptions, namely, that the
largest window radius equals the refilling
radius and that pore volume is independent
of window radius, can be tested together for
the pore space of a random packing of
spheres. Mason (9), in his Fig. 8, gives func-
tions for pore emptying via the largest win-
dow and filling at the pore insphere radius
using the actual tetrahedral pore volumes.
These functions, labeled by Mason I and D1,
have to be identical for the two assumptions
to be exact. In fact they are surprisingly
close together except for the larger values
of curvature (smaller radii).
CONNECTIVITY AND HYSTERESIS
Provided the amount of capillary conden-
sation in an adsorption isotherm can be iden-
tified, the function g(r) can be determined
by using the Kelvin equation to find r from
(P/Po) and by using the volume condensed
as a measure of the number of pores filled.
One might even allow for the thickness of
the gas adsorbed on the pore wall surfaces
but this is a refinement at this stage. The
capillary condensation during adsorption is
a function of g(r) alone because all of the
cavities have access to the condensing vapor
and each fills at its own particular radius.
The cavities en masse behave as an assembly
of independent individuals a n d so experi-
mental measurements of adsorption, the
measurements on a mass, are related to the
function g(r), defined for individuals.
Desorption is different. Not all of the cav-
ities have access to the vapor phase but, for
a cavity to empty (in the absence of cavi-
tation effects), it must have direct access to
the vapor. The desorption process is there-
fore an interrelation between pore space con -~
nectivity and the window radius distribution.
Often a readily identifiable region of de-
sorption isotherms is a pronounced knee. At
 E F F E C T OF P O R E S P A C E C O N N E C T I V I T Y
-- -- -- Limit
0,3.
qcrit
0.2
0 5 I0 15
C connectivity
FIG. 2. The amount o f capillary condensation on the
adsorption branch of an isotherm at the point where the
very steep portion on the desorption branch commences,
qcrlt, is shown as a function of the pore space connectivity,
e. An experimental isotherm can be used to determine
qcr~t, and hence give an indication of the degree of in-
terconnectedness of the pore space.
a value of P/Po above the knee the isotherm
is virtually flat with all the pore space filled
and at a value of P/Po below the knee the
rate at which the volume adsorbed changes
with P/Po is at a m a x i m u m . The " k n e e "
represents a threshold when the pore space
empties in a chain reaction such that the
limited access to vapor by the cavities at the
surface of the assembly is communicated
into the bulk. The analysis is handled easier
in terms of the probability, p, that a window
has a radius less than rp
p =
f0 f(r)dr.
Desorption is now, in effect, the progressive
decrease of p from an initial value of unity
to zero. I f all of the pore space is filled with
condensed liquid there comes a critical value
of p, Petit, when the chain reaction com-
mences. Let the number of meniscus con-
nections in contact with the vapor be y. This
is very small in relation to the total n u m b e r
of cavities and so there will be y cavities,
each with one window in contact with the
vapor. The probability that an individual
41
meniscus does not pass the window to which
it has access is Pcrit and so the probability
that it does pass and e m p t y the cavity is (1
- Pcrit). If the cavity empties then (c - 1)
new windows will have access to the vapor
because there are c windows per cavity and
one has been used to empty it. The total
number of new windows given access to the
vapor is thus
y(1 - Pcrit)(C - - 1)
and for the sustainable chain reaction this
must equal y. Eliminating y and rearranging
gives
Petit = (C -- 2 ) / ( c - 1). [6]
This equation, or its like, must have been
known to Barker (10) in 1958 as he gives
a critical probability, Pcri~, of 0.8 for a six-
connected system in a graph.
The value of P/Po at the desorption knee
can be used to determine the amount of cap-
illary condensation on the adsorption iso-
therm at this point. Let this be qcrit and it
will be given by
qcrit =
f0rcritg(r)dr, [7]
where rcr~ is the radius corresponding to the
critical value of P/Po on the desorption limb.
I f there is no individual pore hysteresis
then Pcrit and qcr~t are linked by Eq. [4] so
that
qcrit : petit \(C -- 1)]" [8]
[t ] The amount of capillary condensed adsorp-
tion at the desorption knee can thus be used
to determine the connectivity of the pore
space. Figure 2 gives q~rit as a function of
c. At c = 2, qcrit is zero because the system
reduces to the "bundle of tubes" model and,
if the tubes are long enough, they e m p t y only
when the smallest window empties. The gra-
dient at c = 0 is zero. The value of qcrit rises
rapidly and reaches a m a x i m u m value as e
----+ o9 o f
((c- 2 ) ~ c = 1/e = 0.3679 [91
.£tc~ \(c- 1)]
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
42
indicating that the amount adsorbed at the
desorption knee can never be greater than
about 36%.
The connectivity of the pore space of var-
ious materials can be expected to lie between
2 (for very consolidated packings of parti-
cles) up to about 14 (for the inverse of sphere
packings, i.e., froths etc.). It can be seen that
qcrit covers most of its range in this region
and so the function is a reasonably sensitive
indicator of pore space connectivity over
most of the useful range and particularly
sensitive in the 2-4 connectivity range.
A P P L I C A T I O N TO L I N D E S I L I C A
It has been shown that the fractional
amount of capillary condensed adsorption at
the desorption knee can be used to find the
connectivity of the pore space. The problem
now reduces to finding the amount of cap-
illary condensed adsorption out of the total
measured amount. The desorption knee is
usually fairly obvious from the experimental
measurements of the desorption isotherm.
One set of data which seems usable is that
of Carman and Raal (11) who measured
adsorption-desorption isotherms of CF2C12
on Linde silica at various degrees of particle
compaction. If the isotherm for the uncom-
pressed material is taken to give the amount
adsorbed on the pore surfaces then the dif-
ference between the isotherm for the com-
pressed material and the uncompressed ma-
terial is the amount of capillary condensation.
The initial sections of the isotherms up to
a value of P/Po = 0.3 are identical indicating
that the surface adsorption is unaffected by
compacting the particles.
The theoretical analysis uses the amount
of capillary condensation in a normalized
fashion such that when the entire pore space
is filled with capillary condensation the
amount is unity and when there is no cap-
illary condensation its value is zero. We
therefore require the fraction of pores filled,
F, as a function of the relative vapor pressure
P/Po. At the same value of relative vapor
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
GEOFFREY MASON
pressure the volume adsorbed can be imag-
ined as being split into two parts: one part
coming from the pores which are completely
filled and the other part from the pores which
contain the variable surface adsorption. If
a particular sample contains N pores and the
average amount of adsorbate per filled pore
is o~ and per unfilled pore is/3 then
Volume adsorbed
= NFa + N ( 1 - F )/3, [101
a will be a constant for the material, inde-
pendent of the relative vapor pressure, but
/3 will vary with relative vapor pressure. For
two isotherms, one for the uncompressed
material, and the other for the compressed
material, let the amount adsorbed per unit
mass at a particular value of relative pres-
sure be M . . . . . p and Mcomp, respectively.
When all of the pores are filled in the com-
pressed sample let the amount adsorbed be
M~oaXp. So MP~o~Xpwill equal Na, the total
number of pores multiplied by the average
amount in each pore and nuncomp will equal
N/3, the total number of pores multiplied by
the amount of surface adsorption in each
pore. So the amount adsorbed by the com-
pressed sample (Eq. [ 10]) can be expressed
in terms of F, and the experimental mea-
surements ( M . . . . . p, M~omp, M~o2
c o mxp p~
Meomp = FM~oam~p+ (1 - F ) M u .... p [11]
or rearranging
F = Mcomp - M .... P. [ 12]
g ~ p -- M .... p
Figure 3 illustrates this diagrammatically
with the two isotherms, one for the uncom-
pressed material and the other for the com-
pressed material. The fraction of the pores
filled is simply the distance AB divided by
the distance AC. Note that the maximum
amount adsorbed by the compressed sample
must be reached at a lower value of P/Po
by the compressed material than the uncom-
pressed material.
 E F F E C T OF P O R E S P A C E C O N N E C T I V I T Y 43

The model advanced here is of an approach

to a chain reaction with a change from the
pore space being emptied only at the surface
to having pores in the interior emptied. It
is clear that a large degree of surface in a
s u r f a c e adsorption i / /
pore system will blunt the edge of criticality.
Also, if a round sample is emptied from the
eJ
outside, successive layers moving in from the
t~ outside contain fewer pores until eventually
o
there is only one pore at the center. This
E
o
E
/ Y
~ _ ~ A
::2:,;;,o.
isotherm
apparent curvature of the pore space con-
nectivity will also round the desorption knee.
<
/ The manner of the progress of desorption in
porous glass observed by Schechter et al.
(12), namely, that a front advances into the
glass with decreasing relative vapor pressure,
i i
I
may have its explanation in this curvature
Relative vapour pressure of the pore space connectivity. Alternatively,
the explanation may simply be that the pore
FIG. 3. A diagrammatic illustration of the method
used to find the fraction (F) of the pore space filled with
space of porous glass is anisotropic.
capillary condensation. O n e isotherm is for an uncom- The precise location of the desorption knee
pressed sample which shows no hysteresis and pore fill- in Fig. 5 can only be inferred but the frac-
ing and the other for an isotherm branch (adsorption
or desorption) from a compressed sample exhibiting
hysteresis.

Figure 4 reproduces the actual data of

Carman and Raal (12) for adsorption and ~,6
desorption on Linde silica powder both un- E
compressed an also compacted into a plug
with porosity e = 0.506. Figure 5 gives the E
transformation, using Eq. [12], to give the 4
fraction of pore space filled by capillary con-
q~
densation, F, as a function of P/Po.
The position of the desorption knee is not
very sharply defined in Fig. 4 and less so in ~2
Fig. 5, the transformed data. There are two
reasons for the rounding of the desorption
O
knee. Schechter et al. (12) explained the E
<
slight slope of the amount adsorbed when all
0
pores were filled as dilation of the capillary o ols i'.o
condensate under the very high stress pro- Relative vopour pressure
duced by the curved liquid/vapor interfaces.
Barker (10) explained the rounding of the FIG. 4. The experimentalresults of Carman and Raal
knee as a surface effect of the first 10 or so (12) showing adsorption of CF2C12at -33.1 °C on two
samples of Linde silica. The reversible isotherm is for
layers of pores as they have more access to adsorption/desorptionon an uncompressedsample and
the vapor than the interior pores. Everett's the isotherm exhibiting hysteresis is for the same ma-
review (13) reinforces Barker's viewpoint. terial compressedinto a plug.
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
44
I ,- . . . . .
F
z~
m Figure 5 can also be used to relate q, which
"8
g equation to a cavity radius size and this is
o of the fractional number of pores filled has
Relative vapour pressure
FIG. 5. The data of Fig. 4 transformed using the
method illustrated in Fig. 3 to give the fraction of the
pore space filled, F, as a function of P/Po. Note that
the desorption knee has become more rounded.
tional amount of capillary condensation on
the adsorption branch indicates a pore space
connectivity of about 4. This is expected as
the material is a compacted assembly of ro-
tund particles and will have a pore space
connectivity similar to that in a random
packing of spheres• If the pore space has a
connectivity of exactly 4 the analysis of
Mason (14) can be applied and this gives the
complete function of the fraction of the pore
space filled as a function of p for desatura-
tion. Mason's (14) analysis is an extension
of the method used here to calculate the on-
set of criticality in desorption but he only
considered a pore space with a connectivity
of 4, whereas here we are concerned with
varying pore space connectivities. The anal-
ysis for fractional saturation as a function
of p, the probability of a meniscus not pass-
ing a window, can be applied to Carman and
Raal's results to find a cumulative window
size distribution• The method involves taking
various values of the fractional pore space
filling on the desorption branch of the iso-
therm in Fig. 5 and relating them to the
corresponding value of p taken from Fig. 3
of Mason's (14) paper. In this way a value
of relative vapor pressure (and hence by the
Kelvin equation a pore size) can be related
to the cumulative probability, p, that a win-
Journal of Colloid and Jnterface Science, Vol. 88, No. 1, J u l y 1982
GEOFFREY MASON
dow is smaller than this size. Figure 6 gives
the values of p as a function of window ra-
dius as calculated from the Kelvin equation
with no attempt to correct for the thickness
of surface adsorbed layers.
equals the fractional pore filling on the ad-
sorption branch, via P/Po and the Kelvin
also shown on Fig. 6. The adsorption branch
,.o been used to determine a cumulative cavity
size distribution (q vs r) and the desorption
branch has been used to determine the cu-
mulative window size distribution (p vs r).
At any value of radius the cumulative cav-
ity size distribution, q, is related to the cu-
mulative window size distribution, p, via the
connectivity, c, such that
q = pC [4]
= 1.0" odsorption
.o •
* desorptiort . ~ "
"T-p,q
m
~3
q3 0.5" ,:~/." /
o
E
g~ o
0 5 I0
rodius (nm)
FIG. 6. The cumulative cavity radius distribution (q
vs r) for Linde silica derived from Fig. 5 using the Kelvin
equation to relate r to P/Pofor the adsorption limb. The
cumulative window radius distribution (p vs r) calcu-
lated from the cavity radius distribution (above) using
a pore connectivity of four and the assumption that the
largest window radius equals the cavity radius is also
shown. The desorption branch of Fig. 5 can be used in
conjunction with Mason's (14) analysis to give the win-
dow radius distribution (p vs r) and also, using a pore
connectivity of 4 and the assumption of the largest win-
dow radius equaling the cavity radius, the cumulative
cavity radius distribution (q vs r). It is the coincidence
of the distributions from the adsorption and desorption
branches that determines the connectivity, c. The di-
vergence for large radii using the desorption branch is
caused by the experimental rounding of the desorption
knee, whereas the theory expects a sharp discontinuity.
 EFFECT OF PORE SPACE CONNECTIVITY
and c, for this particular case is known to
be 4. So a window size distribution can be
determined from the adsorption branch and
a cavity size distribution from the desorption
branch. These are also plotted on Fig. 6. The
degree to which the window sizes and cavity
sizes calculated from the two separate ad-
sorption and desorption branches agree is a
test of the choice of connectivity, Mason's
(14) analysis of the desorption process, and
the assumption of no individual pore hys-
teresis.
DISCUSSION
The application of this analysis requires
the separation of the adsorbed phase into
surface adsorption and capillary condensed
liquid. The example of the analysis of the
pore space in compressed silica is only pos-
sible because the isotherm on uncompressed
powder was available. If no such isotherm
is available then the surface adsorption
across the whole range of relative vapor pres-
sure has to be estimated. The initial portion
of an isotherm up to a relative vapor pressure
of 0.3 is a consequence of surface adsorption
alone and so an extrapolation of the data in
this initial portion of an isotherm to the
whole range of relative vapor pressure will
produce an estimated isotherm of surface
adsorption alone with no capillary conden-
sation. This extrapolation could be done us-
ing the BET equation even though it is gen-
erally accepted that the BET analysis is not
appropriate when the relative vapor pressure
is above 0.3. An improvement might be to
make the BET plot pass through the top clo-
sure point of the actual hysteresis loop, the
theory requiring that it pass to the right.
Alternatively, if the adsorbate is N2 at
-195°C then the empirical t plot of de Boer
(15) derived from many isotherms not ex-
hibiting capillary condensation might be
used.
A crucial assumption has been that of
the largest of the several window radii of a
pore equals the single-cavity radius. Indeed
it is this assumption that makes it possible
45
to relate the adsorption and desorption iso-
therms to each other after allowing for the
different mechanisms participating in the
two processes. That the assumption works
quite well for the pore space of a sphere
packing is interesting but whether it would
work as well for a highly connected pore
space such as that of a foam would seem
doubtful. But the power of this assumption
is the considerable simplification it brings
about in the analysis of capillary conden-
sation hysteresis. Eventually other pore
spaces will be simulated and the error intro-
duced by this assumption assessed. It is
worth noting that if the fraction of the pore
space filled with capillary condensation on
the adsorption isotherm at the desorption
knee is used to determine the connectivity,
c, then one is usually concerned with a frac-
tion of 0.1-0.3 as the value of qcrit- This in-
volves the smaller pores of the distribution
and it is really the degree of agreement be-
tween the cumulative distribution of the ac-
tual pore sizes and the theoretical (calcu-
lated from the desorption windows) in this
region of smaller pores that is important. For
the pore space in a sphere packing it happens
that the agreement is its worst in this region
with the theory predicting smaller pores than
actually occur.
The pore space has been assumed to have
a single connectivity, c, and this is obviously
a simplification as it is likely that there will
be a distribution of connectivity. Perhaps the
simplest way to model this for systems which
are made from assemblies of particles is to
consider each cavity to have c connections
each of which has a probability of being
blocked or closed off. This gives rise to a
distribution of pores with different connec-
tivities and considerably complicates any
analysis. But one is also adding another vari-
able and this is always undesirable.
CONCLUDING REMARKS
The fundamental reasoning that in some
porous materials the main hysteresis comes
Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
46
from the interconnectivity of the pore space
and relatively little hysteresis is due to the
ink-bottle pores and other causes seems to
fit the experimental facts. The model based
on this reasoning gives a not unreasonable
connectivity for the Linde silica case inves-
tigated in detail. Before the method can have
any wide application in determining the
structure of porous materials an accurate
method of determining the amount of cap-
illary condensed liquid as opposed to the to-
tal amount adsorbed, will have to be devel-
oped. The prospect then is that an adsorbent
could be characterized by a single "pore size
distribution" determined from the adsorp-
tion branch and a single "connectivity." To-
gether these parameters would enable the
desorption branch and hopefully even the
scanning curves to be determined.
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Journal of Colloid and Interface Science, Vol. 88, No. 1, July 1982
GEOFFREY MASON
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