164 Langmuir 1988, 4, 164-169

Pressure/Volume/Surface Area Relationships in Foams and

Highly Concentrated Emulsions: Role of Volume Fraction
H. M. Princent
CollGge de France, Physique de la MatiGre Condens&e, 11 Place Marcelin Berthelot,
75231 Paris, Cedex 05, France
Received March 17, 1987. In Final Form: August 17, 1987
Various pressures in and around a foamor concentrated emulsion are discussed in some detail. These
include the internal pressure inside the dispersed cells, the pressure in the interstitial continuous phase,
the disjoining pressure in the films separating the cells, the osmotic pressure, and the vapor pressures of
the dispersed and continuous phases. The effect of the volume fraction, 4, of the dispersed phase is
investigated explicitly, not only on some of the above parameters, but also on the equation of state and
the compressibility of a foam. Earlier results, valid for C$ 1 only, are corrected for 4 <1. The area of
the intercellular films as a fraction of the total surface area and its dependence on 4 have been evaluated
also.
Introduction
The study of foams and highly concentrated emulsions
has seen a resurgence in recent years, partly as a result of
additional potential applications, such as tertiary oil re-
covery by means of such systems. In most published work,
consideration has been limited to situations in which the
volume fraction of the dispersed phase, 4, is extremely
close to unity, such as in dry, polyhedral foams, where
there is negligible continuous phase not only in the thin
films between the bubbles but also in the Plateau borders
along the intersections of films. This is the approach taken
in such studies as those of Derjaguin, Ross,28 Ross et al.,p6
Weaire, Khan and Armstrong? Kraynik and Hansen? etc.
Often this dry foam approximation is appropriate, e.g., in
the top region of a very tall, equilibrated foam or emulsion
column, where the shape of the bubbles or drops indeed
approaches that of fully developed polyhedra with sharp
edges and corners. In many other cases, however, this is
not so, and a more general treatment must incorporate the
volume fraction as a variable in the range $o I 4 I 1, where
$o is the volume fraction of the close-packed, undeformed,
spherical bubbles or drops (Kugelschaum). For mono-
disperse systems, 4o =0.7405; for typical polydisperse
systems, it has been found to be only slightly different and
smaller+12 (not larger as one might expect for some very
specific multimodal size distributions, which, in fact, are
rarely, if ever, encountered in practice).
In a series of recent papers, wehave specifically inves-
tigated the dependence of a variety of static and dynamic
properties on 4, as well as on the drop size and interfacial
Thus, we have shown that the osmotic
pressure,12J 4 shear modulus, and yield s t r es ~~~J ~J ~ all
depend strongly on 4. The same is true for the viscosity,
mostly through the yield stress.l6p2l
In the present study, weinvestigate the effect of C$ on
a number of other properties, such as the internal
pressure in a foam, the equation of state, the compres-
sibility, and the film area per unit volume of the dispersed
phase. We shall also take this opportunity to establish
links between various properties that seem not to have
been made before.
I t will be assumed that the thickness of the films be-
tween the bubbles or drops (the cells) is negligible com-
pared to the cell size (finite film thickness simply gives rise
to an upward shift in the effective volume fraction, as
indicated beforel0J and that the contact angle between
Current address: General Foods Corp., Technical Center, 555
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0143-7463/88/2404-0164$Q1.50/0
the films and the adjacent Plateau borders is zero.
where a is the capillary length
We shall further assume that the cell size is R <<a,
uI2 is the interfacial tension, Ap is the density difference
between the phases, and g is the acceleration due to
gravity. The cell radius, R, is defined as the radius of the
sphere of the same volume as the deformed cell. Because
of the above assumption, the effect of gravity is negligible
with respect to a single cell but plays a role over vertical
distances Az >>a.
The dispersed phase is phase 1; the continuous phase
is phase 2.
Pressures in and around the System
There are a number of interrelated pressures one may
distinguish in a concentrated fluidlfluid dispersion of 4
2 40.
Internal Pressure pi. This is the pressure inside the
cells. If the system is monodispersed and gravity is absent,
pi is identical in all cells. If the system is polydisperse,
the internal pressure will vary from cell to cell, since the
cells are then generally separated by films of nonzero
curvature. In that case one may define an average internal
pressure given by
where pi and vi are the pressure and volume of cell i , V1
(1) Derjaguin, B. V. Kolloid-Z. 1933, 64, 1.
(2) Ross, S. Ind. Eng. Chem. 1969, 61, 48.
(3) Ross, S. Am. J. Phys. 1978, 46, 513.
(4) Nishioka, G.; Ross, S. J. Colloid Interface Sci. 1981, 81, 1.
(5) Nishioka, G.; Ross, S.; Whitworth, M. J. Colloid Interface Sci.
(6) Morrison, I. D.; Ross, S. J. Colloid Interface Sci. 1983, 95, 97.
(7) Weaire, D.; Kermode, J. P. Philos. Mag., [ Part ] B 1983, 48, 245;
(8) Khan, S. A,; Armstrong, R. C. J. Non-Newtonian Fluid Mech.
(9) Kraynik, A. M.; Hansen, M. G. J. Rheol. 1986, 30,409.
(10) Princen, H. M. J. Colloid Interface Sci. 1985, 105, 150.
(11) Princen, H. M.; Kiss, A. D. J. Colloid Interface Sci. 1986,112,427.
(12) Princen, H. M.; Kiss, A. D. Langmuir, 1987, 3, 36.
(13) Princen, H. M. J. Colloid Interface Sci. 1983, 91, 160.
(14) Princen, H. M. Langmuir, 1986, 2, 519.
(15) Yoshimura, A,; Prudhomme, R. K.; Princen, H. M.; Kiss, A. D.
(16) Schwartz, L. W.; Princen, H. M. J. Colloid Interface Sci. 1987,
1983, 95, 435.
1984, 50, 379.
1986,22, 1.
J. Rheol., in press.
118, 201.
0 1988 American Chemical Society
PressurelVolurnelSurface Area in Foams and Emulsions
ATM 0 SPHERE
P
DISPERSION
i Xi Z
.c
Figure 1. Fluid/fluid dispersion in contact with atmosphere.
is the volume of the dispersed phase, V is the total volume,
and the summations are taken over all cells. For a foam,
filled with (ideal) gas, pi represents the pressure inside the
gaseous volume Vl, if all foam lamellae would rupture and
total phase separation would 0ccur.l
We shall return to this pressure in more detail later.
Border Pressure p b. This is the pressure inside the
continuous phase in the plateau borders. I t is related to
pi of a given cell by
Pb =Pi - u121Kbil (3)
where Kbi is the curvature of the free surface of cell i , i.e.,
the surface outside the films. In the absence of gravity,
pb is constant everywhere. In a gravitational field, Pb varies
linearly with height, z, according to
P b =c +Z P g (4)
where C is a constant, p 2 is the density of the continuous
phase, and z is pointing downward. If, as in most practical
situations, the system is in contact with a gaseous at-
mosphere of pressure P at some level z =0, then the value
of C in eq 4 is determined by the curvature, Kt, of the free
continuous phaselgas interface between the dome-shaped
films at the top of the highest layer of cells (Figure l), i.e.,
(5)
In a foam, u2 =u12 is the continuous phaselgas interfacial
tension. (Similarly, for an emulsion in contact with a layer
of dispersed (liquid) phase, u2 =u12 is the liquid/liquid
interfacial tension.) For an emulsion in contact with air,
on the other hand, u2 in eq 5 is the continuous phaselgas
interfacial tension. I t is important to note that, however
complex the detailed shape of the top surface of the system
(particularly in a polydisperse system), Kt is constant ev-
erywhere, even in gravity, provided the surface is hori-
zontally flat on the scale of the capillary length, a.
c =P - U21Ktl
Combining eq 4 and 5 yields
Pb =p - UZIKtl +Z P g . (6)
The second term on the right-hand side is often over-
10oked.~J
It is obvious from Figure 1 that the curvature Kfi at the
top of cell i in the first layer is given by
( 412 +u2)lKfil =c l 2bbi l - u2lKtl (7)
Pi =P +IKfil(Ul2 +UZ) (8)
provided that, in the case of an emulsion in contact with
a gaseous atmosphere, the continuous phase spreads over
and that the internal pressure in that cell is
Langmuir, Vol. 4, No. 1, 1988 165
~ CONT .PHASE(
n:
u
MEMBRANE +
(4 (b)
Figure 2. Semipermeable membraneseparating dispersion from
continuous phase: (a) general view; (b) detailed view of contact
between deformed cells and membrane.
the dispersed-phase droplets in the top layer. If not, a bare
surface of the dispersed phase with tension c1 is in contact
with the atmosphere over some of its area and there will
be a three-phase contact line with the continuous phase
between the drops. Using Neumanns triangle for the
equilibrium between ul, u2, and u12 at the contact line, one
can readily reformulate the problem for this case. The
curvature of the roof of the drops is simply increased by
a factor of (al2 +u2)/u1, while Kbi and Kt remain unaffected.
I t is suggested by Figure 1 that the average relative
internal pressure pi - P inside the system is already fully
established in the very first layer of cells.
The disjoining pressure, IID, is the extra pressure
inside a film due to interaction forces. At equilibrium, it
equals the total capillary pressure acting on the film. For
any one of the films sumunding any cell i (not just a film
facing the atmosphere), it may be written as
where the +and - signs refer to situations where the
convex or the concave side of the curved film is directed
toward the interior of cell i , respectively. In a monodis-
perse system, Kfi is zero everywhere, except for the films
directly facing the atmosphere. When gravity is present,
IKbil and IID then vary linearly with the level z. In a po-
lydisperse system, Kfi, IID, and, therefore, the equilibrium
film thickness vary from film to film, even in the absence
of gravity. This may further complicate the proper de-
scription of the process of foam coarsening by gas diffusion,
where one usually assumes that the thicknesses and,
therefore, the gas permeabilities of all the films are iden-
The osmotic pressure, II, is the pressure that must be
applied to a freely movable, semipermeable membrane,
separating the fluid-fluid dispersion from a layer of con-
tinuous phase, in order to prevent the latter from entering
the di~persion.~J * The membrane is semipermeable in the
sense that it is freely permeable to all the components of
the continuous phase but impermeable to the drops or
bubbles (Figure 2). II equals the pressure exerted on the
membrane by the flattened cells and may therefore be
represented by
tica1.7J8J9
where n is the number of cells per unit area of the mem-
brane and fi is the flattened contact area for cell i .
Previouslylo wehave introduced a total fractional contact
area f:
n
i =l
f = C f i (11)
which can be readily measured optically.1 It is determined
(17) Khristov, K. I.; Exerowa, D. R.; Krugljakov, P. M. J. Colloid
Interface Sci. 1981, 79, 584.
(18) Lemlich, R. Ind. Eng. Chem. Fundam. 1978, 17,89.
(19) Beenakker, C. W. J. Phys. Reu. Let t . 1986, 57, 2454.
166 Langmuir, Vol. 4, No. 1, 1988
primarily by the volume fraction, 4, but may be slightly
dependent on the details of the size distribution.
An alternative expression for II follows from the process
whereby the membrane is displaced downward to squeeze
a volume dV2 of continuous phase out of the dispersion
at constant Vl. For this process one may write
(12)
where S is the surface area in the dispersion. Equation
12 may be transformed into12J 4
II dV2 =-al2 dS
Princen
right-hand side equals -11at the top of the column, while
wemay write for the third term, using eq 6
(20)
where IKtl is the curvature of the free continuous phase/gas
interface at the top of the column (Figure 1).
Thus, by combining eq 19 and 20, weestablish the in-
teresting fact that for the top of the column
P?gH =Po- p +4 4
n =821Kt l (21)
Now, the vapor pressure of the continuous phase above
the dispersion is simply given by the Kelvin equation,
applied to the concave continuous phase/gas interface at
the top, i.e.
p Vc =(PVC)Oe-uziKtIV2/RT =(p$)oe-"V2/RT
(22)
For small cell size and high volume fraction, II tends to
infinity and the reduction in vapor pressure becomes quite
pronounced.
In the case of an emulsion, one may also consider the
vapor pressure of the dispersed phase. It is, of course,
increased relative to that of the bulk dispersed phase. It
can be shown to be given, to a very good approximation,
by
pVd E ( pvd) oe( 2~dR) ( V~/ RT) ( S/ S~)
where (p:)o is the vapor pressure of the bulk dispersed
phase, a12is the liquidlliquid interfacial tension, R is the
drop radius, and Ql is the molar volume of the dispersed
phase. Although p$ depends strongly on R when R - 0,
it is only slightly affected as 4 - 1 through &'/So.
Expressions, similar to the above, may be derived for
the mutual solubility of the phases.
Internal Pressure, Equation of State, and
Compressibility
For a dry, polyhedral foam (Cui =V; 4 =l), Derjaguinl
has shown that the average internal pressure pi and the
equation of state are given by
or
where S/Vl is the surface area per unit volume of the
dispersed phase, S/So is the ratio of the surface area of
the deformed cells and that of the spherical cells of the
same volume, and R32 is the surface-volume or Sauter
mean radius of these spherical cells:
In ref 12 wehave experimentally determined fi and S/So
as a function of for a typical polydisperse system. I t ,was
found that S/ So varies from unity at 4 =c $~ (where II =
0) to 1.083 as 4 - 1 and fI - a.
The vapor pressure, p,", of the continuous phase above
a fluidlfluid dispersion has been reported by us,14 without
proof, to be related to II according to
p Vc =(P v C) oe -nVz/ RT (16)
where (pVc),, i_s the normal vapor pressure of bulk contin-
uous phase, V2 is ita molar volume (or, rather, the partial
molar volume of the solvent), R is the gas constant, and
T is temperature.
Two different proofs will be given here. First, consider
the transfer of dn2 mol of continuous phase from the bulk
to the dispersion. The free energy gained is exactly equal
to the decrease in surface energy in the dispersion as a
result of the accompanying dilution, i.e.
P V C
(PvC)0
Ap2 dn2 =RT In - dn, =a12 dS
(17)
However, according to eq 12, at constant V1
(18)
From eq 17 and 18, one immediately obtains eq 16.
In the second proof, weconsider an equilibrated dis-
persion column of height H, resting on a bulk layer of
continuous phase. We have considered such a column in
detail in ref 12. The values of II and 4 change continuously
with the height in the column. Relative to the atmospheric
pressure, P, above the dispersion, the pressure po =pb(H)
in the continuous phase just below the dispersion must
equal the weight of the column per unit cross sectional
area, i.e.
a12 dS =-11dV, =-IIv2 dn,
From ref 12 and 14 it follows that the second term on the
2 s
p . - p =-a -
3 l 2V
(4 =1)
where pi is as defined in eq 2 and n is the number of moles
of gas in the foam. The same results were later obtained
by Ross.2 Subsequently, Morrison and Ross have pointed
out6 that, although eq 23-24 are strictly valid for mono-
disperse systems and for small clusters of only a few
unequally sized bubbles at 4 =1, their general validity for
multibubble, polydisperse systems has not been rigorously
proven, neither by Derjaguin, nor by Ross himself. They
seem convinced, however, that the equations are exact even
in that more complicated case, and they liken the lack of
a rigorous proof to the situation pertaining to Fermat's
famous last theorem. To avoid this difficulty, let us as-
sume that the system is indeed monodisperse. We shall
remove the restriction on 4, however. It will be allowed
to vary from +o to unity.
With Derjaguin, weconsider an infinitesimal change in
the foam volume, dV =dV,. At equilibrium
Cpi dui - P dVl =a12 dS (25)
Since weassume monodispersity, pi and ui are identical
for all cells, so that
Cpi dui =pi c dui =pi dV1 (26)
1
i I
PressurelVolumelSurface Area in Foams and Emulsions
Therefore
Langmuir, Vol. 4, No. 1, 1988 167
Table I. Terms Involved in Internal Pressure
pi - P =u12( ") dV1 v,
For 4 =1 and an isomorphic change in the cells, one may
write from simple geometric considerations
dS 2s 2s
- =- =-
dV1 ~V I 3V
which, when inserted in eq 27, leads to eq 23.
For do I 4 <1, however, such an isomorphic change is
impossible, as the cell shape must change as Vl and,
therefore, 4 are varied. Equation 28 no longer holds.
Instead, wereplace S in eq 27 by
s =(S/SO)SO (29)
where, as before, So is the surface area of the spheres of
the same volume as the deformed cells of surface area S.
It is clear that S/So is a shape parameter that depends only
on 4, whereas So simply depends on the cell radius.
Hence
Realizing that
wefind from eq 30
Because of eq 14, this may be written in the form
1- 4 2 s
p i - p =- II +-412-
4 3 Vl
($0 I 4 I 1) (32)
where II is the osmotic pressure.
Comparing eq 32 and 23, wesee that for 4 <1 there are
two corrections to Derjaguin's original expression. First,
perhaps intuitively obvious, the surface area per unit
volume of foam, S / V, is replaced by the surface area per
unit volume of the dispersed phase S/ VI =S/$V. Second,
there is a small correction term resulting from the noni-
somorphic nature of the change in cell shape from that of
a sphere to that of a fully developed polyhedron.
Equation 32 can be written in reduced form
where each term depends on 4 only. Although the exact
dependence of fI and S/ So on 4 is not yet known for a
monodisperse system, wehave determined these functions
experimentally for a typical polydisperse system.12 The
results should not differ by very much and may be used
to give excellent estimates of the terms in eq 33. This has
been done in Table I. It is seen that the first term is zero
at both ends of the range, i.e., at =4o and 4 =1. It
passes through a maximum at 4 N 0.965 where it amounts
0.80
0.85
0.90
0.92
0.93
0.94
0.95
0.96
0.965
0.970
0.975
0.980
0.985
0.990
0.995
0.997
0.999
1.000
0.019
0.030
0.041
0.047
0.050
0.052
0.055
0.056
0.057
0.056
0.055
0.052
0.047
0.039
0.031
0.026
0.016
0
2.003
2.009
2.021
2.028
2.033
2.038
2.045
2.054
2.059
2.065
2.072
2.080
2.090
2.102
2.117
2.127
2.142
2.166
2.022
2.039
2.062
2.075
2.083
2.090
2.100
2.110
2.116
2.121
2.127
2.132
2.137
2.141
2.148
2.153
2.158
2.166
to about 2.8% of the value of the second term.
In the limits, wehave
2 s 2 s
pi - P =-412- =-412-
3 V 1 3 V
(4 =1)
which is identical to Derjaguin's result, and
2 9 2
R
p i - p = - (4 =40)
as expected for spheres.
alized equation of state of the foam
which leads to
Using the result of eq 32, wemay write for the gener-
piVl =nRT (34)
or
4V =nRT (36)
For the limit of 4 =1, Derjaguin has also evaluated the
compression modulus K, which is defined as
His result is
This compares with K =P for a simple, ideal gas. As with
the previous expressions, eq 37 has been rigorously proven
only for monodisperse systems. With our previous results,
it can now be generalized for 4 <1. We find for the
compression process at constant V2
K =-(P 1 +2p;) +- (' ,4)2( - z)vz
(38)
34
where pi is given by eq 32 or 33. It is noted that the
derivative in the second term is at constant volume of the
continuous phase, which implies a change in the cell radius
R. It can be shbwn that
168 Langmuir, Vol. 4, No. 1, 1988 Princen
Table 11. Terms Involved in Eauation of State
2
(1 - b)2.
b 3b)n ( d n / d b ) 4/3(S/SJ C
0.715 0 0.048 1.333 1.381
0.75 0.003 0.050 1.334 1.387
0.80 0.006 0.054 1.335 1.395
0.85 0.010 0.057 1.339 1.406
0.90 0.014 0.062 1.347 1.423
0.92 0.016 0.066 1.352 1.434
0.93 0.017 0.067 1.355 1.439
0.94 0.017 0.067 1.359 1.443
0.95 0.018 0.065 1.363 1.446
0.96 0.019 0.060 1.369 1.448
0.965 0.019 0.057 1.373 1.449
0.97 0.019 0.052 1.377 1.448
0.975 0.018 0.046 1.381 1.445
0.98 0.017 0.038 1.387 1.442
0.985 0.016 0.034 1.393 1.443
0.990 0.013 0.028 1.401 1.442
0.995 0.010 0.020 1.411 1.442
0.997 0.009 0.016 1.418 1.443
0.999 0.005 0.010 1.428 1.443
1.000 0 0 1.444 1.444
((1 - b ) /
where fI is the reduced osmotic pressure.
Hence, one ultimately finds
which, because of eq 32, may be written as
12 dfI 4
=++ &-=I - $ - +(1 -$)Z- +- - )] (41)
4 d@ 3 so
where the terms inside the large parentheses depend on
@ only. As before, these may be estimated from the data
in ref 12. This has been done in Table 11. As was seen
for the internal pressure pi, the Derjaguin _term in S/ S,
is much more important than the terms in II and dfI/d@.
The main correction is the factor l/@ in front of the square
brackets.
Total Surface and Film Area
In ref 12 and 14 wehave shown how the total surface
area of a fluid/fluid dispersion increases as the volume
fraction is raised from @o to 1. This information can be
derived from n(@), which, in turn, may be determined
experimentally from the variation of the volume fraction
with height in an equilibrated emulsion column. Thus we
have found for a typical, polydisperse emulsion that the
transition from spheres to polyhedra is accompanied by
an increase in the specific surface area of the dispersed
phase, S/Vl , of 8.3%, i.e., S(l)/So =1.083. At any stage,
a fraction of the total surface is free, while the comple-
ment, Sf/S, is the fraction that forms part of the films
separating the droplets. Obviously, Sf / S varies from zero
at @o to unity at @ =1. Detailed knowledge of its depen-
dence on @ is important, as it clearly plays a role in
problems relating to the stability of, and mass transport
in, such systems. For example, the rate of coarsening of
a foam by gas diffusion will be primarily proportional to
Sf, since the gas diffuses almost exclusively through the
films. The same may be true for the rate of coalescence
in relatively unstable systems.
For convenience, again assume the system to be mono-
disperse. Each cell, of volume u and total surface area s,
is contained in a polyhedron of volume up and area sp (up
>v; sp >s). This polyhedron tessellates in space. It is
clear that
u/up =4
For the purpose of this discussion, it is not essential to
speculate on the exact shape of the polyhedron. At the
lower volume fractions, it is probably a rhombic dodeca-
hedron, while Kelvins minimal tetrakaide~ahedron~ is
more likely at higher 6.
Now consider another polyhedron, somewhat smaller
than but isomorphous with the first, whose volume is upl
=u. Its surface area spl is the same as that of the cell at
@ =1:
I t is clear from geometric considerations that
up =u =@up
spl =s(1)
so that
2/3 S( I.) /So
=(:) s/s,
1.083
-
- -(S/S0)-1 @2/3
where S/So is known from experiment, albeit for a poly-
disperse system.12 I t is not expected to be very sensitive
to the size distribution, however.
To obtain the fraction Sf / S of the total cell area that
is locked up in the films, wewrite
Now, careful consideration of the compressive forces that
are responsible for the deformation of the cells leads one
to the conclusion that sf/sp exactly equals the fraction of
a confining wall that is taken up by the flattened parts of
the cells pushing against it. This fraction, f , has been
discussed above; see eq 11. I t also has been measured
experimentally on a typical, polydisperse system.1 Em-
pirically, it was found to depend on @ as
(43)
3.20
112
f ( 4) =1 -
(A +7.70)
between 4,, and 4 =0.975. For @ 2 0.98, weexpect, on
theoretical grounds,14
(4 2 0.98) (44) f ( 4) =[l - 1.892(1 - 4)lI2I2
Thus, replacing sf/sp by f in eq 42, weobtain
(45)
where f ( 4) and S/So are known, at least approximately.
A plot of Sf / S vs @ is shown in Figure 3.
Discussion
We have seen that the volume fraction in concentrated
fluidlfluid dispersions has a profound effect on some
properties, e.g., the shear modulus, yield stress, osmotic
pressure, disjoining pressure, vapor pressure of the con-
tinuous phase, specific film area, and fractional contact
PressurelVolumelSurface Area in Foams and Emulsions
Figure 3. Surface area in T i s, as fraction of total surface area.
area of the cells against a confining wall. Other properties
are less affected, e.g., the internal pressure (relative to the
external atmosphere), the equation of state, and the vapor
pressure of the dispersed phase.
It appears that the recently introduced concept of os-
motic pressure, and its measured dependeme on $, are
extremely useful in describing and evaluating other system
parameters.
If there is one uncertainty remaining in this and previous
work, it is the lack of detailed knowledge as to the effects
of polydispersity and size distribution. We are inclined
to believe, with Morrison and ROSS, ~ that at least some
results are unaffected by polydispersity, but a rigorous
proof is lacking. A closely related question has to do with
the proper mean drop radius that is to be used to char-
acterize a polydisperse system. We believe that in most
cases it is the surface-volume or Sauter mean radius, since
most properties are determined by the specific surface area
S/VP In other cases, this is less obvious, however. Since
a detailed theoretical analysis of polydisperse systems is
extremely complex and unlikely to be forthcoming soon,
the more promising avenue is the experimental one, pro-
vided one employs systems that are well characterized in
terms of their size distribution, volume fraction, and in-
terfacial tension. Of primary importance would be the
experimental determination of n($) and f ( $) for mono-
disperse, as well as a variety of well-characterized poly-
disperse, systems, both unimodal and multimodal.
An interesting and important recent finding20 is that
S(l)/So =1.097 for Kelvin's minimal tetrakaidecahedron,
which is the ideal cell in a monodisperse system at $ =1.
Since our experimental value for a typical unimodal po-
lydisperse system is S(l)/So =1.083, this provides strong
evidence that, contrary to our previous assumption,12 po-
lydispersity may give rise to a decrease in S(l)/&.
(20) Princen, H. M.; Levinson, P. J. Colloid Interface Sci. 1987,120,
(21) Princen, H. M.; Kiss, A. D. J. Colloid Interface Sci., submitted.
172.
Langmuir, Vol. 4, No. 1, 1988 169
Acknowledgment. I thank Professors P. G. de Gennes
and A. M. Cazabat for helpful comments.
List of Symbols
capillary length, (alz/Apg)l/'
numerical constant
fractional area of "contact" of cells and adjacent
contact area for cell i
acceleration due to gravity
height of foam or emulsion column
index for cell i
compression modulus for foam, -V(dP/dV),,
moles of gas in foam
moles of continuous phase
ambient pressure above foam or emulsion
pressure in continuous phase just below foam or
emulsion column
pressure in continuous-phase Plateau borders
pressure inside cell i
average pressure inside cells
vapor pressure of continuous phase above disper-
vapor pressure of bulk continuous phase
vapor pressure of dispersed phase above dispersion
vapor pressure of bulk dispersed phase
gas constant
radius of sphere of same volume as deformed cell
surface-volume or Sauter mean radius of cells in
polydisperse system
surface area of single cell
surface area of single cell at 4 =1
surface area of circumscribing polyhedron of single
surface area of polyhedron of same volume as a cell
total surface area in system
total surface area in system at 4 =4o
total surface area in system at 4 =1
fraction of S forming part of intercellular films
temperature
volume of single cell
volume of cell i
volume of circumscribing polyhedron of single cell
volume of polyhedron of same volume as cell (=u)
total volume of system, Vl +V,
volume of dispersed phase
volume of continuous phase
molar volume of dispersed phase
molar volume of continuous phase
height in foam or emulsion column, measured from
curvature of free surface of a cell
curvature of free continuous phase/gas interface
curvature of intercellular films
chemical potential of continuous phase
osmotic pressure
reduced osmotic pressure, rLR32/u12
disjoining pressure in intercellular films
density of dispersed phase
density of continuous phase
P2 - P1
surface tension of dispersed phase
surface tension of continuous phase
interfacial tension between dispersed and contin-
volume fraction of dispersed phase
volume fraction of close-packed spheres
wall
sion
cell
top down
at top of system
uous phase