Pore size analysis according to
the Kelvin equation
J.M. H A Y N E S (1)
The theoretical and practical principles underlying the
determination of pore size distribution from measurements of
the capillary condensation of vapours are reviewed. As in
mercury porosimetry, a model must be introduced to provide
a simplified description of the pore structure, and the two
methods are similar in principle. However, rather elaborate
corrections are necessary to take account of multimolecular
adsorption which accompanies capillary condensation. Never-
theless, the method is suitable for pores too fine to be measurable
by mercury porosimetry. The range of applicability of the
Kelvin equation, the process of micropore filling and the origin
of adsorption hysteresis are reviewed briefly.
1 - INTRODUCTION
1.1 - Capillary condensation
When a vapour is physically adsorbed on the
surface of a non-porous solid with which it has a
reasonably strong attractive interaction, the adsorpt-
ion isotherm is generally of the kind known as Type II
in Brunauer's classification [1]. That is to say, it is
sigmoid in shape, the gradient increasing at high
relative pressures, as multilayer adsorption succeeds
completion of the monolayer.
(1) School of Chemistry, University of Bristol, England.
If, however, the solid contains accessible pores
between roughly 2 and 20 nm in diameter, the nature
of the isotherm changes markedly, becoming character-
istically of Brunauer's Type IV. As the pores begin
to fill, the chemical potential of the absorbate is
reduced not only because of proximity to the solid
surface (adsorption forces) but also as a result of the
formation of negatively curved, or concave, menisci
within the pores (capillary condensation). Adsorption
is therefore enhanced in this region, as the pores,
beginning with the smallest, fill in succession. When
all the pores are filled, only the external surface of the
porous solid remains to support multilayer adsorption;
the gradient of the isotherm therefore decreases
suddenly, and adsorption reaches a more or less sharp
upper limit as the saturation vapour pressure is
approached. The volume adsorbed at this limit is
equal to the pore volume of the sample (Gurvitsch's
Rule).
A further difference appears when the capillary
condensate is removed by desorption : the Type IV
isotherms exhibits hysteresis. This phenomenon,
which implies that a given quantity of capillary
condensate may be distributed within a pore system in
more than one equilibrium way, can arise from various
causes. In constructional materials, the two most
important mechanisms underlying capillary condensat-
ion hysteresis are (i) non-uniform pore geometry,
209
VOL. 6 - N ~ 33 - 1973 - I H A T i ~ R I A U X ET
within which liquid/vapour interfaces may pass
spontaneously between alternative configurations,
driven by capillary forces, and (ii) swelling and
shrinkage effects, whereby the pores may change
theil shape during the processes of filling and empty-
ing. In both cases, it can happen that pores, or groups
of pores, fill and empty at different relative pressures,
giving rise to hysteresis.
The principal differences between adsorption on
non-porous and porous solids were illustrated very
clearly by the experiments of Carman and Raal [2],
shown in figure 1.
1.2 - The Kelvin Equation
The variation of vapour pressure with liquid/vapour
interracial curvature is governed by the Kelvin
equation :
RT
- - ln p / p ~ = a C
v
where p0 is the saturated vapour pressure exerted by
bulk liquid adsorbate, having a plane surface, at the
absolute temperature T, and p is the vapour pressure
over a surface of mean curvature C. R is the gas
constant, and v and a are the molar volume and
surface tension of the liquid, respectively. The mean
curvature C is defined as the sum of the reciprocals
of the principal radii of interracial curvature rl and r2 :
C_ _1 + _1
rl r2
1.3 - Pore models
The basis of the method of pore structural analysis
by capillary condensation is the adoption of a relation-
ship between the interracial curvature C and the
dimensions of the pore. By this means, equilibrium
at a given value of p/pO can be associated with pores
of a particular size. This necessitates the introduction
of a model to specify the geometry of the pores. For
example, if a cylindrical pore of radius r is assumed,
then one possible configuration of the liquid/vapour
interface formed within it will be a portion of a sphere
of curvature
2 cos 0
C -- (3 a)
r
where 0 is the contact angle formed by the liquid/yap-
our interface at its intersection with the pore wall.
Alternatively, if the pore is assumed to be slot-shaped,
with parallel walls a distance d apart, then the interface
will be cylindrical, with curvature
2 cos 0
C -- d (3 b)
In the absence of evidence to the contrary, cos 0 is
usually taken to be 1.
Equations (3 a) and (3 b), or elaborations of them
(see Section 3.1), provide the necessary link between
pore size and interracial curvature, and hence (via the
Kelvin equation) relative vapour pressure. Identical
equations, based on the same models, are used in the
interpretation of measurements of mercury penetrat-
tion and suction porosimetry.
210
CONSTRUCTIONS
12
a~
--g 10
E
g
o
"-o 1
#
1
i!
/
i i i i
0.2 0.4 0.6 0.8 1.0
p/p~
(1)
Fig. 1. - - Measurements by Carman and Raal of adsorption
of CF2C12 on Linde silica powder at - - 33.1 oC. The loosely-
packed powder gives a Type II isotherm (full line), but after
compaction a Type IV isotherm with hysteresis (dashed line)
is obtained, indicating the occurrence of capillary condensation
in the interparticle spaces.
(2)
1.4 - Micropore Filling
If the pore diameter is only a few times the molecular
diameter of the absorbate, the Kelvin equation cannot
be expected to hold, and indeed the very existence o f
a liquid/vapour meniscus, and of a heterogeneous
mechanism of pore-filling, becomes untenable. Inst-
ead, such micropores are thought to fill by a homo-
geneous mechanism [3]. If the opposing walls of a
pore are so close together that their adsorption fields
overlap, then the whole pore may be regarded as
forming part of the adsorption space, and it will
become filled with adsorbate in that range of relative
pressures, too low for the existence of a liquid-like
condensed phase, in which monolayer and multilayer
adsorption would take place on non-porous surfaces.
Thus, such pores will appear more as an extension o f
the surface of the solid than as a part of the pore
volume.
Pores in this size-range are very often found in
cements and plasters, where their formation is closely
linked with hydration reactions.
2 - PRACTICAL M E T H O D S OF M E A S U R I N G
CAPILLARY C O N D E N S A T I O N
Capillary condensation may be studied by exper-
imental methods essentially identical to those used in
the measurement of specific surface by gas adsorption,
that is, volumetric and gravimetric methods. These
have been reviewed elsewhere in this volume by
Fagerlund [4], and will not be described here in detail.
The following points should, however, be noted.

(i) The volumetric method is not ideally suitable
for measurements on materials of large pore volume,
since the dosing in of large quantities of vapour is
tedious to perform, and increases the incidence of
cumulative errors. Moreover, in such cases, the
relatively large quantities adsorbed enable less sensit-
ive and less elaborate gravimetric methods, such as the
McBain spiral balance, to be employed with advantage.
At a more sophisticated level, gravimetric systems can
be adapted to fully automatic operation, producing
results of high precision [5, 6].
(ii) Methods of measuring adsorption in which
mixtures of the adsorbate and an inert carrier gas are
caused to flow past the sample are generally unsuitable
in the capillary condensation region.
(iii) A wide choice of adsorbates is available.
However, since it may be necessary to control and
maintain vapour pressures close to saturation, especi-
ally when examining rather wide-pored samples, the
adsorption of nitrogen at its boiling-point is not
recommended, even though it is commonly used in
specific surface measurements. The reason is that,
unless an elaborate cryostat system is used, fluctuations
in the boiling point of the liquid nitrogen used as
refrigerant, arising both from the solution of impur-
ities and from variations of atmospheric pressure, may
cause unacceptable fluctuations in the saturation
vapour pressure within the system. This problem can
be avoided by using such adsorbates as butane at
0 ~ or tetramethylsilane at 15 or 20 ~ Because of
its specific interactions with many materials of practic-
al interest, water may be an interesting adsorbate,
especially when compared with other, more inert
adsorbates. This possibility has been t.tilised, for
example, by Brunauer and co-workers [7-9] in their
comparative studies of water and nitrogen adsorption
by cement pastes.
(iv) In order that the solid under examination may
be exposed to vapour pressures up to saturation, it is
essential that the region surrounding the sample should
be colder than any other part of the system.
(v) When hysteresis accompanies capillary condens-
ation, it is necessary to establish the boundary curve
of the hysteresis loop. It is therefore essential that
adsorption measurements should be carried up to the
adsorption limit at saturation vapour pressure before
desorption is begun, and that desorption should also
be completed without premature reversal.
3 - I N T E R P R E T A T I O N OF M E A S U R E M E N T S
3.1 - Multilayer Film Corrections
At a given value of the relative vapour pressure p/pO,
filled pores will contain liquid/vapour interfaces whose
curvature, C, is given by eq. (1). At the same time the
surfaces of unfilled pores will be covered by a multi-
layer adsorbed film whose mean thickness, t, will
also be a function of pip o. We assume that the relation-
ship between t and p/pO can be established empiric-
ally by measuring the multilayer adsorption isotherm
of the same adsorbate on a non-porous sample of the
same adsorbent of known specific surface, and making
J.M. H A Y N E S
an appropriate assumption concerning the density
of the adsorbate in the multilayer film. There are two
corrections which may now be applied to the interpret-
ation of capillary condensation measurements.
In the first place, the radius of curvature of the
hemispherical meniscus in a cylindrical pore, the so-
called Kelvin radius
rK = 2/C (4)
(compare eq. (3 a)) will be less than the pore radius r by
the thickness of the multilayer film :
r~ : r - - t (5)
where t and C in eq. (4) and (5) both correspond to the
same value of p/pO.
Secondly, a decrease of relative pressure, from (p/pO)t
to (p/p~ will not only empty pores whose Kelvin
radii lie between (rK)1 ~-- rl - - tl and (rK)2 = r2 - - t2,
but will also entail a partial desorption from the
walls of all pores of radius greater than re, where the
multilayer film will decrease in thickness from tl
to t~. The volume of adsorbate desorbed in this second
process is given by the product of (tl - - t2) and the
area of the multilayer film pores of radius greater
than r2. Once again, the calculation of the appropriate
area demands the introduction of a model to define
the area/volume ratio of the pores.
Brunauer and co-workers [10, 11] have pointed out
that the second of these corrections may be applied
without reference to any specific geometrical model,
if an independent estimate can be made of the area
of exposed multilayer film in the unfilled pores.
He has suggested that the area of this surface may be
calculated from the work done in its formation,
which in turn is obtained from an appropriate integral
over part of the adsorption isotherm. This procedure
is not entirely free from criticism [12] : in principle,
the basic thermodynamic analysis employed is valid
only for reversible processes, whereas the processes
giving rise to hysteresis in capillary condensation are
irreversible; and in practice, it is necessary to assume
that the multilayer film has the same surface tension
as bulk liquid, an assumption so far unsupported by
experimental evidence. Nevertheless, the Brunauer
" model-less " method has been successfully employed
to investigate the pore structure of several materials,
including silica [13, 14], carbon [15], and cement
pastes [7-9, 16-18], and it is claimed that the results
show an internal consistency which supports the
validity of the method.
An alternative to the Brunauer treatment has recent-
ly been put forward by Radjy and Sellevold [19], but
no application to experimental results has yet been
reported.
3.2 - Limits of Applicability of the Kelvin Equation
Practical considerations place an upper limit on the
range of pore sizes which can be investigated by
capillary condensation. Unless considerable care is
taken, the relative vapour pressure p/pO cannot be
controlled with adequate accuracy above a value o f
about 0.98. According to eq. (1), this corresponds to a
cylindrical pore diameter of very roughly 150 nm,
for most adsorbates.
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VOL. 6 - N ~ 33 - 1973 - M A T I ~ R I A U X ET
The existence of a lower limit may also be inferred,
since the macroscopic thermodynamic principles
upon which the Kelvin equation is based must ultimate-
ly break down when the pore diameter is not more
than a few times the molecular diameter of the adsorb-
ate. Even before this stage is reached, the physical
properties of the adsorbate (surface tension and
density) may differ sufficiently from the bulk properties
to introduce appreciable errors in calculation of pore
size [20].
Evidence exists, however, that the lower limit is
reached much more suddenly than would be expected
on the basis of such considerations. Harris [21, 22],
for instance, has shown that when average pore radii
calculated from the Kelvin equation are compared
with those obtained from the ratio of twice the pore
volume to the specific surface, reasonable agreement
exists, for a wide range of materials, down to a pore
radius of about 1.8 nm. Almost no Kelvin radii
below this size were observed, however. Since there
is no reason to suppose that pores smaller than this
cannot exist, it seems likely that the Kelvin equation
fails abruptly at this point. It has been suggested [23,
24] that a stable condensed phase cannot exist in
such very small pores, because of the negative pressure,
or tension, to which it is subjected. Presumably, it is at
about this stage that the homogeneous process of
micropore filling, mentioned in section 1.4, supervenes.
3.3 - Computational Procedures
Because of the multilayer film corrections outlined
in Section 3.1, the calculation of a pore size distribut-
ion from capillary condensation measurements is
rather tedious. Early procedures were suggested by
Barrett, Joyner and Halenda [25], Cranston and
Inkley [26], and many other authors using similar
principles. A discussion and comparison of some of
these methods is given by Irving and Butt [27].
It is of great assistance if regularly-spaced experimental
points are available. Since these are difficult to obtain
in practice, it may be preferable to fit the experimental
measurements to an analytical curve and employ
numerical interpolation, especially if computing
facilities are available. Computer programmes for
calculating pore size distributions according to the
various procedures available have been developed by
several authors [28-30].
The Brunauer model-less method involves an integra-
tion which, in the original work, was performed
graphically. This has now been replaced by an analytic-
al integration [31], and a Fortran IV programme has
been written to carry out the entire procedure of pore
size analysis [32].
212
CONSTRUCTIONS
4 - DISCUSSION
Methods of pore size determination based on
measurements of capillary condensation are essentially
similar in principle to the mercury porosimetric
method, in that both depend ultimately on the deter-
mination of the curvature of a fluid interface within
a pore. However, whereas this curvature is manifested
as a hydrostatic pressure difference in the porosimetric
method, capillary condensation methods rely on the
much smaller influence of curvature on vapour
pressure. This has the result that very large curvatures
(very small pores) correspond to inconveniently large
hydrostatic pressures, and are therefore more access-
ible to capillary condensation than to mercury porosi-
metry. On the other hand, the vapour pressure reduct-
ion in larger pores may be too small to measure.
The two methods are therefore complementary.
In the region where the two methods overlap, good
agreement has been found between them [33, 34].
Partly because of the very much larger curvatures
that are encountered in capillary condensation
measurements, such methods suffer from complications
not met with in mercury porosimetry. The most
important of these are the corrections which must
be made to allow for the simultaneous occurrence of
capillary condensation and multilayer adsorption.
As measurements are extended to the smallest pores,
so both the properties of the capillary condensate and
the mechanism by which pores fill and empty are
liable to undergo changes which are, as yet, imperfect-
ly understood. Ultimately it becomes difficult to
define, either conceptually or experimentally, what is
meant by the size or the volume of pores of molecular
dimensions, although their existence may be clearly
demonstrated by, for example, molecular sieving
action.
Capillary condensation and mercury porosimetry
have the common characteristic that the pore size
distribution that they measure is founded on a model
which represents both the shape and the mode of
interconnection of the pore space in a greatly over-
simplified way. Irregularities of pore shape, and pore
blocking effects, are neglected. It is thus not un-
expected that these two methods should give concord-
ant results. A far more interesting possibility is that of
comparing information gained from capillary condens-
ation and from methods of altogether different prin-
ciple, such as fluid flow. Disagreements between such
measurements can, in principle, yield information on
the extent and nature of deviations of real systems from
model behaviour, which would go undetected if only
one type of observation were made.

RI~SUMI~
Etude de la porosit6 selon l'6quation de Kelvin.
On d~crit le processus de condensation capillaire des
vapeurs dans des pores de dimension intermddiaire
(mdsopores, de l'ordre de 2-20 nm). On examine les
causes de l'hyst&~sis d'adsorption et le mdcanisme par
lequel m~me des pores plus petits (micropores) se
trouvent remplis. La distribution du diam~tre des pores
peut 6tre calcuHe au moyen d'un modkle gdomdtrique
simple, ?t l'aide de l'dquation de Kelvin. On se sert d'un
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J.M. HAYNES
modkle identique pour interprdter les mesures de
porosimOtrie au mercure ; les deux mdthodes donnent des
rdsultats concordants. La condensation capillaire peut
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de eeux qui sont accessibles ~ la mdthode au mercure.
Cependant, il faut des corrections assez complexes
pour tenir compte de l'adsorption multimoldculaire qui
accompagne la condensation capillaire. On prdsente les
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213