Entropy-Induced Dispersion of Bulk Liquids ~

H. REISS
Department of Chemistry, University of California, Los Angeles, California 90024
Received March 17, 1975; accepted July 8, 1975

The possibility that two-phase fluid systems will emulsify spontaneously, due to entropy
effects, is investigated theoretically. It is discovered that for interfacial tensions below about
2 dynes/cm, such spontaneous dispersions can occur, although with large tensions
the dispersed particles are not macroscopic. However, for interracial tensions below 5 X 10 -4
dynes/cm, macroscopic particles are formed.
Spontaneous dispersion due to entropy effects is to be distinguished from the formation of
micellar solutions that form because of energetic considerations.

1. INTRODUCTION micellar solutions in which the micelles are

Everyone knows that two immiscible liquid
phases can coexist at equilibrium. Because of
gravity, the denser phase is always found at
the bottom of the fluid system. Even in the
absence of gravity, the system, at equilibrium,
would consist of essentially two fragments,
each corresponding to a phase whose location
would be neither fixed nor predictable.
If the binary system has an upper consolute
(critical) temperature, a broader range of
fragmentation occurs at that point and the
clear distinction between the two phases
disappears. The fluid then consists of clusters
ranging continuously in size from macroscopic
lumps of both phases down to individual
molecules. However, even here, in the presence
of gravity, stratification occurs.
All of this raises an interesting question.
Are there situations, possibly in ternary
systems, in which the fluid, in the absence of
gravity, would prefer to disperse, at equi-
librium, into macroscopic fragments much
larger than molecules rather than remain in
one cohesive lump? The answer is affirmative;
the situation at the critical temperature is a
case in point. Furthermore, there are so-called
1Research supported under NSF Grant No. MPS73-
04743-A01.
quite large, if not macroscopic, clusters of one
of the original phases. The motivating in-
fluence for the formation of micellar solutions
is largely energetic. For example, a typical
micellar solution may consist of fatty acid
and water (1). By dispersing as micelles, the
fatty acid molecules are able to increase the
area of contact between their polar heads and
water while maintaining their fatty hydro-
phobic tails in close association. However, it is
conceivable that there is another driving force,
besides dispersion. This is the entropy gained
by the act itself. Such entropic effects also are
present in the micellar case, but are usually
unnecessary in view of the prior effects of
energy.
Ordinarily, dispersion is thermodynamically
unfavorable because the extended interface
between the two phases occasions an untenable
increase in interface free energy. While the
"entropy of mixing" that results from dis-
persion produces a reduction in free energy,
it is rarely enough to overcome the increase
due to the interfacial effects. As a result,
spontaneous dispersion does not occur. Micellar
solution may be crudely regarded as a case in
which the interfacial tension is negative so that
extension of the interface leads to a decrease in

61
Copyright ~ 1975 by Academic Press, Inc. Journal of Colloid and Interface Science, Vol. 53, No. I, October 1975
All rights of reproduction in any form reserved.
62
free energy, and no further decrease (e.g., free
energy of mixing) is required to effect dispersion.
I t is natural to ask whether cases exist in
which the interracial tension is positive, but
small enough that the increase in interface free
energy can be overcome by the mixing free
energy so that dispersion occurs. Dispersion
at the critical point is a limiting example of
this phenomenon; it is well known that the
interracial tension tends to vanish as the
critical temperature is approached.
Recently, there have been reports (2) of the
development of surfactants capable of reducing
interfacial tensions at an oil-water interface to
the range 10 -4 to 10.5 dynes/cm. One wonders
whether or not such a low interracial tension is
enough to cause spontaneous dispersion. Such
an end result could have a profound impact
(ignoring economics) on technological processes
like tertiary recovery.
In the remainder of this paper, we perform
a statistical thermodynamic analysis of the
possibility of such "entropy-induced" disper-
sions in systems where the interfacial energy
is small, but still positive.
2. A SIMPLE MODEL
The question raised at the end of the previous
section can be studied conveniently by model-
ing the dispersed fragments as spherical drops
of one phase possessing the interfacial tension
corresponding to the fiat interface, even though
the drops may be very small, e.g., consisting
of several thousand molecules. We denote the
two phases by the subscripts 1 and 2, reserving
the 2 for the less abundant phase, which we
also regard as the dispersed phase. If the
interracial tension is denoted by ~, and we
assume that the chemical potentials of both
components are not changed by dispersion,
the change in free energy associated with
such a process (ignoring the free energy of
mixing) will be
AG' = ~ N,4~rri2~,
i of the clusters will be estimated, essentially,
where Ni are the number of drops of phase 2
of radius r~. If ~ is positive, G will necessarily
Journal of Colloid and Interface Science, Vol. 53, No. 1, October 1975
H. REISS
be positive and spontaneous dispersion will
not occur.
However, as indicated in the last section,
there is another contribution, &G", which
comes from mixing, so the change in free energy
should be
a a = ~G' + a a " . E2~
If &G" is sufficiently negative, the net change
&G will be negative, leading to a dispersed
equilibrium state. We therefore attempt to
calculate zXG".
In performing this calculation, we note, as
it has been recognized before (3), that a
spherical cluster of fluid not fixed to the
laboratory frame of reference (e.g., not like a
drop suspended from a capillary tube, itself
at rest in the laboratory frame) must be defined
thermodynamically by a Gibbs dividing
surface centered on its center of mass. Thus,
the spherical clusters in our model will have
this property. In contrast, a "drop" to which
the surface tension ~ refers, is fixed to the
laboratory frame, and the dividing surface
used to define it is similarly fixed. Thus, in a
drop the position of the center of mass may
fluctuate with respect to the dividing surface.
The thermodynamic properties of the cluster
may therefore (as we shall show) be estimated
from those of the drop, but they are not
precisely the same.
To make matters even simpler, we assume
that when dispersion occurs, clusters of only
one size (one value of radius) are produced.
Since the entropy of mixing would only be
increased by admitting clusters of many sizes,
the tendency towards dispersion could only be
increased. Thus, an estimate based on clusters
of one size gives a lower limit for the influence
towards dispersion. If dispersion is indicated,
the phenomenon is even more likely when
many sizes are allowed.
Our general procedure will be equivalent to
the following. The "internal" partition func-
[1-] tions (motion relative to the centers of mass)
by referring them to the free energies of a
laboratory drop of the same size. The spherical
 DISPERSION OF LIQUIDS
clusters will not be considered statistically
inflependent but will be allowed to interact
through their centers of mass. This interaction
will take the form of familiar interaction
between "hard spheres" of radii equal to that
of the clusters. The configurational partition
function of the disperse system then becomes
identical to that of the equivalent hard sphere
system for which very good estimates are
available. This theory is developed in the
next section.
3. PARTITION FUNCTION OF THE DISPERSED
SYSTEM
We begin by dividing the system into two
subsystems corresponding roughly to the two
phases, 1 and 2, and to which we assign the
respective partition functions, (21 and Q2.
Subsystem 2 is assumed to include the interface,
i.e., the surface free energy is assigned to phase
2. Furthermore, we assume that the partition
function for the total system is given by
Q = Q1Q2,
an approximation not unreasonable as long
as effects due to the interaction of the two
systems can be largely subsumed into surface
effects invariant to the configuration of the
clusters of the dispersed phase.
If ~1 is the chemical potential in phase 1 and
there are N1 molecules in that phase, then
the Helmholtz free energy of the phase is
A1 = N1~I - pV1,
where p is the pressure and V1 is the volume
of the phase. Then,
(21 = exp(--A { k T )
= e x p 1 - - - ( N l ~ l - - pV1)/kT].
The evaluation of Q2 is considerably more
involved. Suppose there are N2 molecules in
phase 2. Because of the assumed independence
of the two phases or subsystems implicit in the
product in Eq. (3), we may proceed with the
system of iY2 molecules as if it alone were
63
present in the total volume
V = Vl -t- V2 [6]
of the system. V2 is the volume of phase 2.
These molecules are assumed to be partitioned,
always, between ND clusters, each containing
n molecules. The clusters are spherical, and
are defined by the requirement that all of the
molecules in a given cluster lie within a
distance r of the center of mass of the group
comprising the cluster (4, 5). The magnitude
of r is determined by
r = (3nv2/4~r)~, [7]
where v2 is the volume per molecule in bulk
liquid phase 2. Thus, r is chosen as the radius
of a drop of phase 2 consisting of n molecules.
Then the cluster resembles a drop but differs
from it by the fact that its boundary surface
(dividing surface) is fixed relative to the center
of mass, whereas in a drop the center of mass
can fluctuate with respect to the dividing
[3] surface.
As indicated in the last section, the molecules
within a cluster may interact with each other
by means of normal intermolecular forces, but
the interaction between clusters will be
governed by the potential,
u~s = ¢(l~r..ll~), [S]
where UHS is the potential for ND hard
1-4] spheres of radii r and R1 through RND are the
coordinates of the centers of mass of the
clusters. The logic behind this is the following.
The clusters represent quasi-macroscopic (or
macroscopic) fragments of an emulsion (dis-
persion). As such, it is sufficient to account for
1-5-] their configurationai properties by disallowing
overlaps between particles. The hard sphere
potential specified in Eq. [-8] takes care of
this. Interaction within a cluster is accounted
for by the ordinary intermolecular potential,
while that between the clusters and phase 1 is
accounted for by the surface free energy.
With these conditions, it is possible to
Journal of Colloid and Interface Science, Vol. 53, No. 1, October 1975
64 H. REISS

write Q~ as and Q2 can then be represented by (3, 4)

Q,, . . . . exp[-fl ~ p.2

__~ [.. \ j=l 2m \N2 !hsN~/\ (n ])NOND !)/

x dr~...drxJm...dpze~. [93
X
L L .. exp I - - f i e ( R e . . RND)]

X lI exp --fl
In this equation, rl and pl, etc., are the co- i=i 2m
ordinates of position and momentum of the
N2 molecules (which for simplicity we assume +
to be structureless and devoid of internal
degrees-of-freedom), U(rl.-.rN,) is the po- X dr~(i)dpl (~).. .dp,/~) 1 [125
tential for molecular interaction within clusters,
¢ is the hard sphere potential defined in
Eq. [8], m is the mass of a molecule, in which we allow contributions to the integral
h is Planck's constant, and/3 is 1/kT, where k only when each set of r l ( i ) " • ' r , S ) have values
is the Boltzmann constant and T is tem- such that
perature.
[ry) -- R~[ < r, [13]
The potential U can be represented by the
sum
where r is given by Eq. [7]. Eq. [13] implies
i=ND that any r/i) lies closer than the distance r to
U= ~ Ui(r1(~)--'r,Jl)), [10] the center of mass of the ith cluster. In Eq.
[12], the condition, Eq. [13], could be applied
where U~ is the potential for molecular inter- by simply introducing potentials which pass
action within the ith cluster, and (rl (o. . •rn (o) to infinity when the inequality in Eq. [13] is
are the coordinates of the molecules within violated. However, the condition is so simple
that cluster. This follows from the assumption that it is enough to state it.
that the interaction between clusters is deter- Next we transform to center of mass co-
mined by ¢(R1". "RN~), so that there are no ordinates (4, 5). Thus, we introduce r/~)' by
cross terms in U between clusters. For a fixed the relation
set of locations, rt (o.. .r~ (ND) (and conse- r/i) = r/i)' + R~, j = 1,2...n- 1, 04]
quently a fixed set of R1." "RND), there is a
large number of permutations of the N2 where
molecules which correspond to the same value
1 J=~
of the integrand in Eq. [9]. However, permu- ll~ = - E C i). [153
tations that permute "whole clusters" must n j=l
not be counted since these are accounted for
by the integration in Eq. [9-1. The molecules In terms of these coordinates, we may write
are of course considered distinguishable, the
actual indistinguishability being corrected for, Ui(rl(O...r. (1)) = fi(rl (i)'.. .rn_l(1)'), [16]
as usual, by the 1/2V2[ preceding the integral
in Eq. [9-1. The proper number of permutations since the molecular interaction can only depend
may easily be shown (4) to be given by on the internal coordinates of the cluster.
Substituting Eqs. [-14-1-1-16] into [12"], inte-
grating over the momenta, and performing
Journal of CoUoid and Interface Science, Vol. 53, No. 1, October 1975
 DISPERSION OF LIQUIDS 65

some algebraic condensation, yields

Q2
<°f £
. . . . .
NvtY
dRy.., d R ~ e~p [ - - ~ ( R 1 . . . R~)-]

X II . . . . exp E-flfi(rl (i)'.-.rn_l(i)')-]dri <i)'...dr~-i (°' [-17~

i< / n[ J o

. . . . dR1.., dRND exp [ - - ~ 4 , ( R v ' ' Rx~)-]

@ ~f
ND! fv
T,,-lna
[
X .
t n!
. _.
J /.
.
~.
exp
. [--¢~f(ri'. "r~-i)-]dri
' ' . . • d r~_l '
7 . [-18]

In this equation, nv2 is the volume of the
cluster. The integration is limited to this
volume by the condition, Eq. [-13]. The
quantity, % resulting from the integration over
momenta, is
"y = (2~rmkT/h2)~,
i.e., the reciprocal of the de Broglie wavelength
for a molecule of mass m. In passing to the
last form in Eq. [-18-], use has been made of the
fact that all the integrals in the continued
product are identical and the i subscript and
superscript could be dropped. The n 3 in Eq.
[-18-] comes from the Jacobian of the trans-
formation from laboratory to center-of-mass
coordinates (4, 5).
As a point of reference, it might be men-
tioned that if q~ were set equal to zero so that
the individual clusters did not interact with
one another (an ideal gas of clusters) and the
transformation back to laboratory coordinates
were made, the result would be
a distance r of their common center of mass
are allowed.
Comparison of Eq. [-18-] (with ~ = 0) with
Eqs. [-20-] and [-21-] reveals that
[-19-1
4
M dri'.., dry-1' I I [-223
Now, within the framework of our model, we
wish to evaluate the quantity in braces in
Eq. E22-] (for use in Eq. [-183) by reference
to the free energy of a "drop" of n molecules.
The partition function of a drop, fixed in the
laboratory frame of reference, may be expressed
by a formula very similar to Eq. [-22-]. To
avoid confusion, we denote this partition
function by X~. Then we have (4),

Q~ = q~N~/X~ !, E20-] X =~f dRI7'~-l___

na
where nv~ L n!

qn
=':/ L
n! - exp[- --Su(rl. • •r,) -]
X drl...drn, [-211
X L ( m " • • f exp [--Sf(rl'" • •r~-l)-]

X dr[. • •dr~_l } i [23-]

and represents the classical phase integral of
a single cluster. Here the integral is over the The differences between Eqs. [ 2 2 - ] and [-23]
entire volume V, but it is understood that in are the following.
performing the integration, only those con- Because the bounding or dividing surface
figurations in which all n molecules are within of the drop is no longer centered on the center
Journal of Colloid and Interface Science, Vol. 53, No. 1, October 1975
 66 H. REISS

of mass, the volume over which the center-of- Comparison of Eqs. 1,26] and [27-] then yields
mass coordinates r~'.., rn_, ~ go in the integral
in Eq. 1,23-] will be a function of R (5). We
indicate this by symbolizing the limits of
integration by v(R) rather than nv2 as in Eq. z(R)dR
1,22-]. In addition, in Eq. [23-] the integration
J!
t,.~ nv2
over R is limited to the volume, nv2, of the where P (0) is the probability density measuring
fxed drop, rather than extending over V as it the chance that the center of mass will be
does in Eq. 1,22]. found at the origin. Substitution of Eq. [29-]
We can also write Eq. [23-] in the form into Eq. 1,28-] gives
standard for the partition function of a fluid
of n molecules confined to a volume nv2, "in-in3 f J]~
namely, n! "'" v2exp [---/sf(rl'...r~-l')-]
X . = ('i./n!)Zn, 1,24]
X drl'-..dr,_l' -- z(0) = - - P(0), 1,30-]
where z. is the configurationalpartition function n[ 7
for n molecules confined to nv2. Comparison of
Eq. [24] with Eq. 1,23] shows that and substitution of Eq. [30] into [-181 yields

z'~=f~,2dRI n 3f~(m exp[--/3f(rl'...r.-l')]

FXnP(O)y
f(..
X drt'..-dr~_l' 1 . 1,25-] × exp 1,-/3~(R1... RNv)~dR1... dRN~. [-31]

Now the Helmholtz free energy of a drop

Clearly, the quantity in brackets in Eq. [-25] consisting of n molecules of phase 2 may be
is the configurational partition function for a expressed as
drop under the constraint that its center of
mass is held at the point R. Denoting this
an = n#2 + O~n~ pnv2, 1,32] - -

configurational integral by z(R), Eq. 1,24-] in which u2 is the chemical potential in phase 2
becomes at temperature T and pressure p (note that
the pressure inside a drop may differ from the
Xn = z(R)dR. 1,26-1 pressure p outside), and a is given by
v2
a = 47r~(3v2/47r)~, 1,33"1
Since the integral over the center-of-mass
where ~ is the surface tension. In the canonical
coordinates in Eq. 1,22-] refers to the case
ensemble, a~ is related to the partition function
where the center of mass is constrained to the
k~ by
center of the spherical volume, nv2, i.e., to the
case R = 0, we can write a~ = -- (1//3) in Xn, [34]
so that combining Eqs. [32] and [34] gives
"In/V "In
q" n! z(0)dR n] Vz(O). 1,27] X~ = exp[--fl{n#2 + an~ -- pnv2}-]. 1,35]
The quantity P (0) has been estimated with
Furthermore, the quantity in braces in considerable accuracy, in another context
Eq. 1,22] is clearly (3, 4) to be
"in--1
- -
nt
z(0) =
~n
--
~V
1-283 P(0) = -- 1 I~r( 6n )'1'
, 1,36-]

Journalof Colloidand InterfaceScience,Vol. 53, No. 1, October 1975

 DISPERSION OF LIQUIDS 67

where (7). Defining

f = p/po, [37] y = 4rrraC/3 [-43]

in which p0 would be the density of the fluid and

if the quasi-hard cores of the molecules were = 4~rr3~PHs/3kT, [44]
close packed and p is the actual density. For this expression is
most liquids, f approximates 0.5, and typically,
y + y2 + ya

P(o) . .
, .r,2,7
.
n; (12)' [38]
= -

(1 - y)~
[4S]
nT)2 L. 71" .A T2 \ 7 1 " ] "
Substitution of this relation into Eq. [40]
With both M~ and P (0) determined, it remains and subsequent integration yields
to evaluate the integral in Eq. [31]. We
accomplish this in the next section.
ZHS= {
V(1--y) exPL2(l_y)Mj E<
4. T H E HARD SPHERE CONFIGURATION
INTEGRAL AND FREE ENERGY OF TIlE Thus, we have expressed ZHS as a function of
TOTAL SYSTEM N•, r, and V.
Substitution of Eqs. [35], [38], and [46]
The integral in Eq. [31] is simply the into [31] then yields,
configurational partition function for N•
hard spheres of radii r confined to the volume
V. We denote it by ZHs(ND, V). Now the
hard sphere equation of state may be expressed
in the form
(O lnZns~ , X exp [ - - ( ~ T ) { n u 2 q-au2 q-an~--pnv2,]
pH~ = kT 7V / T , ~ [393
ray(y - 2)-]} N~,
X V(1 -- y) exp l . . . . / 1-47]
from which we easily derive, by integration, L 2(1 -- y)2_l
the formula
where we have substituted 1/kT for 5. Finally,
ND substituting Eqs. [5] and [47] into [3] gives,
Nit S
Co for the total partition function of the system,

r
X exp --fiND
u. d CO
p~s(C) , [40] Q = exp --
kT ND!

in which X exp -- (1 -- y)
C = ND/V [41] ( V2

and
Co = lim C. [42] X exPL2(1 -- y)~dJ ' [48]
V -->~o

Co is of course zero, but we retain it in Eq. where we have used the relations
[40] because it is not immediately clear that
it introduces no singularity. : Y D n = IV'2 [-49]
and
Now an excellent analytical expression for
N~n~2 = V~ [50]
PHS (C) is available from scaled particle theory
(6), and confirmed by Percus-Yevick theory together with Eq. [6].
Journal of Colloid and Interface Science, Vol. 53, No. 1, October 1975
68 H. REISS

Although the system is in equilibrium, ~1 is AG', and AG", the free energy of mixing is
and ~ are different because they refer to
different species. Actually each phase is a
binary solution and ~ and #~ are separately AG"=--kTND l n t v2 (l--y)
equal in each phase. However, both phases
are assumed dilute so that the bulk free
J E55]
F3y(y - 2) -I 1 1-]
energy of phase 1 is essentially N ~ and that X exp [ - - --~-a-~2J/ -- in ND +
-2y(1 - y)
o

of phase 2, N2~2. We are ignoring the small

contributions from the attenuated solute in For spontaneous dispersion to occur, it is
each phase. necessary that
The Helmholtz free energy of the system
is then AO < O. [-561

A = - - k T In Q We investigate this possibility in the next

section.
= N1~1 + N2~2 - - p V

5. QUANTITATIVE ESTIMATES
-- k T i n - -- exp [--an~/kT-]
ND[ v2 \ T r ~ The quantitative consequences, for disper-
sion, may be quickly discerned through an
/
x (1 - y ) e x p - -
V3y(y- 2)7j}~,
- Z E511 application of Eq. [-53]. In this analysis, we
I_2(1 -- y) will regard the interracial tension ¢ which
enters the equation through a in the manner
and the Gibbs free energy is prescribed by Eq. [-33] as the controllable
variable. At constant temperature, such a
G = A + p V = N l # i + N2#2
variation of ¢ will require the addition of a
third component, a surfactant, to the system.
-krln 7o! L ,7) We can assume that the surfactant is strongly
localized to the surface, and that it is able
to reduce the surface tension (when enough
X (1 -- y) exp [_)~ - - y - ~ j . [52-] of it is present) to such small values as 10-4 to
10.5 dynes/cm. The general approach will
involve expressing AG in Eq. [53] as a function
The last term on the right side of Eq. E521 is of n, and determining what value of n will
AG of Eq. F21, N1~1 + N2~2 being the free cause AG = 0. Any smaller value of n will
energy before dispersion. We may express this then require AG < 0, and spontaneous dis-
term as persion will be indicated.
AG = an+ND On the other hand, it must be borne in mind
that the maintenance of ~ at a constant low
level as dispersion occurs will require the
G . (l-y) addition of more surfactant since more surface
will be generated. Therefore, to achieve the
equilibrium state of dispersion characteristic
× exp [3y(y--_ 2)1/ -ln V + 1] E531 of a given constant ¢, a very large amount of
surfactant may be required. To express AG or,
from which it is evident that equally convenient (since N1) is positive),
A G / N D as a function of n, we make use of the
a n i N D = 4~rr~aN z) [-541 relation ND = N2/n, Eq. [-491. In addition,
Journal of Collold and Interface Science, VoI. 53, No. 1, October 1975
 DISPERSION OF LIQUIDS 69

we note that from Eqs. [41] and [-43], TABLE I

~r n r
y = 47rraC/3 = 41rraND/3V (dynes/cm) (molecules) (ern ) (sites/par ticle)
= nv2Nv/V = nv2N2/Vn
1.68 10 6.20 X 10-s 2.25 X 10
= v2.¥2/V. [57] 1.00 102 1.34 X 10-7 1.04 X 102
3.53 X 10-1 103 2.88 X 10-7 4.84 X 102
S u b s t i t u t i n g Eqs. [--33] and [48] into, [53] 1.06 X 10-1 104 6.20 X 10-7 2.25 X 103
and setting AG -- 0, gives 2.91 X 10-2 105 1.33 X 10-6 1.04 X 10*
7.64 X 10-3 106 2.87 X 10-6 4.84 X 104
kT(4~) I Ve (12n')I 1.94 X I0-3 107 6.19 X 10-6 2.24 X 105
,r=-- in - - -- (l--y) 4.82 X 10-4 10s 1.33 X 10-5 1.04 X 106
47r t v2.¥2 \ ~r / 1.18 X 10 -4 109 2.87 X 10 -5 4 . 8 4 X 106
2.83 X 10-~ 10~° 6.19 X 10-5 2.25 X 107
6.73 X 10-~ 10n 1.33 X 10-4 1.04 X 108

T h e relationship between n and ~ in this a typical value, then

equation is just that required in order to have
V = (N1 + N2) X 10-22 cm a
AG = 0, so for a n y given value of ~, a value
of n smaller t h a n that required b y Eq. [-58-] = 2N2 X 10-22 cm a. [-60]
causes the system to be dispersed. We also set T = 300°K. With these choices,
To make matters simple, we choose each
phase to have the same volume per molecule y = 0.5, [-61-]
in the liquid and assume also that N1 = N2. and Eq. [58] becomes
If we choose
v2 = 10-2~ cm 3, [-59] 3.974
z = - { ( 1 . 5 0 0 I n n ) -- 1.490}. [62-]
n{
1011
Table I was prepared using this equation.
1010 I n the first column, values of interfacial
tension are provided. The second column lists
109
values of n for the particles that will arise
because of spontaneous dispersion at the
108
values of ~ appearing in the first column.
107 Column 3 gives the radius in centimeters of
the particles listed in the second column,
rl 106
assuming v2 = 10-22 cm a. Finally, the fourth
column lists the n u m b e r 2; of "surface sites"
10~
on each particle, assuming each site to occupy
304 the area @. Fig. 1 is a plot of n versus ~,
based on the data in Table I.
103
We note t h a t spontaneous dispersion is
indeed predicted for interfacial tensions below
10~
about 2 dynes/cm, and t h a t above this value
! no dispersion occurs. However, at 1.68
10
10 6 ~0 5 104 10 3 10"2 10 1 100
O-{DYNESI'CM) d y n e s / c m , the particles will hardly be macro-
scopic, containing only 10 molecules. On the
FIG. 1. Plot of the equilibrium size (number of
molecules in particle) of the dispersed particle as a other hand, at 1.17 X 10-4 d y n e s / c m , the
function of interfacial tension. clusters will contain 109 molecules and have a
Journal of Colloid and Interface Science, Vol. 53, No. 1, October 1975
 70
radius approximating a third of a micron.
These will be quite macroscopic.
The last column gives some idea of the
amount of surfactant that will be required.
Assuming the surfactant molecule localized to
the surface and occupying one surface site
as defined above, we see that, to achieve
dispersion, particles containing 109 molecules
will require 4.84 ;< l0 G surfactant molecules
per particle, or a mole fraction of about 0.005.
In closing, we should note that the clusters
will be in dynamic equilibrium. If they are
small enough, they may disappear at one
point only to reappear at another. However,
quasi-macroscopic clusters are likely to main-
rain continuous identities. Furthermore, when
the surface tension becomes quite small, the
thickness of the interfacial region will increase
to the point where it becomes comparable to
the dimensions of the cluster. In this limit, our
Journal of Colloid and Interface Science, VoL 53, No. 1, October 1975
H. REISS
model becomes quite inadequate, and it m a y
be necessary to view the calculated results as
qualitative at best.
REFERENCES
1. HAI~TI~EY,G. S., "Progress in the Chemistry of
Fats and Lipids," Vol. 3. Pergamon Press,
London, 1955.
2. Private communication, NSF Workshop on Tertiary
Recovery, Austin, Texas, June 1974.
3. REISS, H., in "Nucleation" (A. C. Zettiemoyer,
Ed.), Vol. 2, Sect. 8, to appear.
4. REISS, H., in "Nucleation" (A. C. Zettlemoyer,
Ed.), vol. 2, Sects. 9, 10, to appear.
5. REISS, H., KATZ, J. L., AND COHEN, E. R., Y. Chem.
Phys. 48, 5553 (1968).
6. REISS, H., "Advances in Chemical Physics" (I. Pri-
gogine, Ed.), Vol. 9, p. 53. Interscience, New
York, 1965. Also, REISS, H., FI~ISCH,H. L., AND
LEBOWlTZ,J. L., J. Chem. Phys. 31, 369 (1959).
7. WE~I~EI~, M. S., Bull. Amer. Phys. Soc. 8, 329
(1963).