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130 J. E. Leibner and J.

Jacobus

Charged Micelle Shape and Size

J. E. Lelbner and John Jacobus*


Department of Chemistry, Clemson University, Clemson, South Carolina 2963 1 (Received August 12, 1976)

Pubfcation costs assisted by NIGMS, US. Public Health Service

The shape of micelles incapable of attaining spherical geometry has previously been discussed in terms of an
oblate ellipsoidal model. Calculations are presented which indicate that this model is most probably incorrect,
the correct model being a hemisphere capped cylinder. This latter model is discussed relative to available
experimental data.

Introduction where v is the volume of the tailof an individual monomer.


Although numerous studies of micellization have ap- Both Tartar’ and Tanfordlo have previously presented
peared in the literature’ and although the gross charac- expressions for the length (1) and volume (u) of surfactant
teristics of micellar catalysis of various chemical processes monomers in terms of n,, the number of carbon atoms in
have been described,2relatively fewer studies have been the surfactant tail. Although the expressions presented’
conducted in which the major emphasis centered on the by Tartar are essentially equivalent to those of Tanford,’O
size and shape of micelles. Prior to 1955, the major models we shall employ those of Tanford which consider half of
considered were spherical and lamellar.3-7 In 1955 Tartar the head group-a carbon bond in the chain:
describeds an ellipsoidal model for aggregated surfactants
which, due to constraints introduced by the length of their
+
1 = 1.5 1.265n, 8, (2)
hydrocarbon chains (“tails”), were thought incapable of and
aggregation to spheres. This same model was subsequently
adoptedg and refined‘O by others. v = 27.4+ 26.9nCA 3 (3)
In 1959 Tartar concluded” that numerous systems For the spherical model, employing 1 as the radius, N,
previously described8by the oblate ellipsoidal model were, as a function of n, is presented graphically in Figure 2. At
in fact, spherical. A similar conclusion has been more the core surface (radius = 1) the surface area per monomer
recently reiterated12by others. Within the confines of the is essentially invariant (Figure 3). In general, however,
models chosen it is abundantly clear that a spherical model interest lies in the surface area per monomer (SAIN,,,)
cannot accommodate micelles of large aggregation num- at some distance 1 + d, where d is the distance increment
ber?JOi.e., shape alteration must occur. Micelles incapable from the core to the polar head grou s. For the sake of
of adopting spherical shape have been modeled8-’0 as
oblate ellipsoids.
comparison we have chosen d = 2.0 1
The surface area
per monomer (head group 2.0 A removed from the hy-
A second model for nonspherical micelles, a cylinder drocarbon core) is also presented in Figure 3. A marked
possessing a diameter twice the length of the tail of the decrease in SAIN,,, is noted as n, increases. The net
constitutent monomers, originally proposedt3by Debye and effect expected upon increasing n, is to increase head group
Anacker, has been employed by others, e.g., Stigter,14but, repulsions. In order to counteract this increased repulsion
to our knowledge, no comprehensive comparison of this it should be expected that if surfactants micellize to
latter model to the ellipsoidal models has appeared. In spherical shapes the number of monomers required to form
view of extensive experimental evidence13J5J6that the a “stable” micelle should increase as n, increases (provided
cylinder is the most probable shape of a number of micellar that the electrostatic repulsive interactions dominate the
aggregates, we have performed such an analysis. The desolvation energy of the hydrophobic tails) and/or that
results are reported herein. the fraction of charge (the fraction of “free” counterions)
should decrease as n, increases. We shall return to these
Models points subsequently.
Upon micellization in water the hydrocarbon chains of Granted that certain micelles are incapable of assuming
surfactant ions are removed from the surrounding solvent spherical geometry and that a change in shape is therefore
and, concurrently, the charged head groups become required, those shapes should be preferred which afford
proximate. A priori, a number of assumptions concerning the greatest possible surface area per monomer at the polar
the micelle are required to construct a model, viz., (1)the head groups. Tartar* and Tanfordlo have suggested an
interior of the micelle (core) should resemble bulk hy- oblate ellipsoid (the solid of revolution generated by
drocarbon; (2) the charged head groups should be as widely revolution of an ellipse about its minor axis) as a possible
separated as possible to minimize electrostatic interactions; model and have demonstrated that N,, can be markedly
(3) voids should not exist in the core; and (4) little, if any, increased by minor changes in the axial ratio (nlll = n in
solvent should exist in the core.17 These assumptions, Figure 1). It should be noted, however, that any increase
previously employed by others,8~10,’2 allow comparisons of in the axial ratio ( n > unity ( n = unity for the sphere))
shape and size to be made for various micelle models. must perforce increase the core volume and consequently
If the minimum extension for any model is chosen as increase N,,,. The question that remains is whether or
1 (Figure l),the core volumes of the models (V)are readily not the oblate ellipsoid, within the constraints of our
calculated. The maximum number of monomers (Nmax) original assumptions, affords greater surface area per
capable of occupying these volumes are monomer than any other reasonable model.
Although a cylindrical model (rod) was considered by
N,,= v/u (1) Tanford,’O the model chosen was unreasonable in the sense
The Journal of Physical Chemistw, VoL 81, No. 2, 1977
Charged Micelle Shape and Size 131

Figure 1. Micelle model dimensions for sphere, oblate spheroid, 5 10 15 20


hemisphere capped cylinder, and bilayer. Cross hatched = head group
“C
volume.
Figure 4. Surface arealNmx for sphere (S), ellipsoid (E), and cylinder
(C) at I + 2.0 A.

140 I I I
/ include hemispherical end caps, a reasonable model
emerges; this model is readily generated from the sphere

I 1
(“Hartley m i ~ e l l e ” by
) ~ growth of a cylindrical body of
radius 1 (“Debye-Anacker model”)13 within which the
monomer packing resembles that of the monomers found
about any great circle of the original sphere.
For any axial ratio n of an oblate ellipsoid (major
100
semiaxis = nl;minor semiaxis = l ) , it is readily shown that
at constant volume the length h of the corresponding
hemisphere capped cylinder (Figure 1)is
4
h = - l ( n 2 - 1) (4)
3
Quantitatively, it can be shown that at the core surface at
constant volume the difference in surface area between a
hemisphere capped cylinder and an oblate spheroid is

(5)
where n and t are the axial ratio and eccentricity, re-
8 12 16 20 spectively, of the ellipsoid. The surface area of an oblate
“C
ellipsoid will exceed that of a hemisphere capped cylinder
of equal volume (semiminor axis = cylindrical radius =
Figure 2. N,,, as a function of n, for spherical micelles.
hemisphere cap radius = I ) if and only if
4

100 a condition which cannot be met for any value of t.


Similar, but more complex expressions have been derived
at a distance d from the core surface ( I d); the hemi- +
sphere capped cylinder exhibits greater surface area than
the oblate ellipsoid of equal volume for all values of d. The
constant volume constraint was chosen such that Nm,,-
(cylinder) = N,,,(ellipsoid) and it is therefore obvious
(inequality 6 ) that the surface area per monomer of the
cylinder exceeds that of the ellipsoid.
For the sake of comparison we have chosen core volumes
of ellipsoids and cylinders twice those of the sphere of

6ot
I
8 12
,
16 20
-
equal n,. The generated models possess at least one di-
mension in common with the corresponding sphere (radius
of sphere = semiminor axis of ellipsoid = radius of cylinder
and radius of hemisphere- cap). Thus, the surface area per
monomer for the sphere of volume V is compared with the
“C
ellipsoid and cylinder of volume 2V (containing 2N,,,
Figure 3. Surface arealNmaxat /(lower) and at I + 2.0 A (upper). monomers) in Figure 4. The ellipsoids have semimajor
axis equal to d21 (eccentricity = 0.707) at the core surface
that the ends of the cylinder were uncapped, i.e., the and varying eccentricity at a distance increment d of 2.0
hydrocarbon tails on the cylinder ends were exposed to A. At d = 2.0 A the hemisphere capped cylinder possesses
solvent. If the cylindrical model is slightly modified to greater surface area per head group than the corresponding
The Journal of Physical Chemlstw, Vol. 8 1, No. 2, 1977
132 J. E. Leibner and J. Jacobus

4
t B

1.5 3.0 1.5 3.0 _”


n 0 2 4 6 8 10
N x 10 -3
Figure 5 . Surface arealmonomer at I + 2.0 A for the cylindrical (C)
and ellipsoidal (E) model: (A) n, = 10; (6)n, = 20. Flgure 6. Surface area/monomer at I + 2.0 A for a c16 micelle as
a function of Nagg.
TABLE I : Surface Area Per Monomer for Bilayer
(Surface area/monomer), A ’ creases in surface area per monomer. Up to Nagg of ca. lo4,
n, t ( A ) = 21 Single chain Double chain the surface area per head group has not reached values
required (predicted on the basis of the model) for bilayer
8 23.24 20.87 41.74 formation (Table I).
10 28.30 20.95 41.90
12 33.36 21.00 42.00 Tanford, by ignoring the effects of the ends of cylinders,
14 38.42 21.03 42.06 concluded’o that micelles undergo spherical to oblate
16 43.48 21.06 42.12 ellipsoidal to cylindrical shape alteration. Our analysis
18 48.54 21.08 42.16 indicates that the ellipsoidal model is inferior to the
20 53.60 21.10 42.20 hemisphere capped cylinder (Debye and Anacker model)I3
in terms of available surface area per polar head group.
oblate spheroid of equal core volume (equal Nmax),The We are aware of the fact that the increased surface area
ratio ASAc-E/N,,, is ca. 1.9 A’ per head group. per head group is a consequence of the cylinder end caps.
Similarly, comparison of cylinders with oblate ellipsoids We will show that this model is reasonable and consistent
of equal core volume as a function of axial ratio (eccen- with a large body of experimental evidence.
tricity) leads to the conclusion that as the axial ratio
becomes large (approaches 3.0; eccentricity approaching The Question of Chain Length
unity) the ratio ASAc-E/Nmaxbecomes larger. These So far in our discussion we have not addressed the
results are depicted in Figure 5 for n, = 10 and 20; at n question of the number of chain atoms considered to be
= 3 and d = 2.0 A the values of ASAC-E!N,, are 8.99 and contained in the core of the micelle. Tanford has
7.76 A’ per head group, respectively. Similar calculations suggestedlO that n, should not represent the entire hy-
reveal that the prolate ellipsoid is inferior to the oblate drocarbon tailbut, rather, due to decreased hydrophobicity
ellipsoid, i.e., at constant core volume the surface area per of the carbons proximate to the head group, that the two
head group is less for the prolate model than for the oblate carbons adjacent to the head group be excluded in the
model. Although the surface area per head group dif- calculation of the dimension 1. Stigter has more recently
ferences between the hemisphere capped cylinder and the suggested1’ that the whole hydrocarbon chain be con-
oblate ellipsoid model are small at small eccentricities sidered in the core of micelles, Le., that the hydrophobicity
(Figure 5), we believe that the cylindrical model is superior of all carbons is essentially equal and that solvent in-
to an oblate or prolate ellipsoidal model when the main terpenetration of such micellar cores is minimal.
consideration is surface area per head group. The actual determination of chain length for inclusion
The bilayer model chosen is similar to that of Tanford.lo in a micellar core has been a point of contention; Schott
For the model depicted in Figure 1 reached the conclusionQthat most micelles in aqueous
v = ts2 (7) solution at the critical micelle concentration (cmc) could
not be spherical. This claim was subsequently refuted”
where t = 21. For any aggregation number (iVagg)of by Zografi and Yalkowsky on the grounds that Schott
monomers employed unreasonably short chain lengths. Tartar, in
V = N,,(27.4 + 26.9nC) contrast to his earlier conclusions,8 subsequently
(8) concludedll that numerous micelles were spherical at the
If the monomer possesses two hydrophobic tails, the cmc in the absence of supporting electrolytes.
volume must be multiplied by a factor of 2. The results Recent experimental evidence, e.g., laser Raman
are presented in Table I for monomers possessing one and spectroscopylBand 13Cspin-lattice relaxation
two hydrophobic tails. Single chain surfactants possess indicates that near the polar head group the hydrocarbon
only half the surface area per monomer available to the chains of micelles exhibit a fair degree of rigidity. If this
corresponding double chain surfactant. The exceedingly rigidity is interpreted as evidence for a preferred anti
low values of surface area per monomer for single chain conformation of the chain near the head group, then re-
surfactants, approaching those of hydrocarbons in the gardless of the length of chain chosen to exist in the core,
crystalline state, would appear to preclude transitions from the locus of the head groups must be 1 + d , where 1 is the
“normal” micelles (cylinders) to bilayer (or vesicle) ge- maximum chain extension. In this regard the arguments
ometries. advancedlO by Tanford to reduce aggregation numbers of
Granted that the cylindrical model is applicable to micelles by reduction of the number of chain atoms
normal micelles, we have graphically depicted the surface contained in the core are open to question.
area per monomer for a 16 carbon amphiphile as a function If a reduced core is described by n, - 2 carbon atoms and
of the aggregation number (Figure 6). After an initial if the excluded two-carbon “fragments” are radially ex-
rapid decrease of surface area per monomer (to Naggca. tended away from the reduced core surface so as to afford
500), further large increases in Naggresult in small de- maximum separation of head groups, a void volume
The Journal of Physical Chemlstty, Vol. 8 l, No. 2, 1977
Charged Micelle Shape and Size 133

TABLE 11: Aggregation Numbers of


Micelles at Cmc in Water
Surfactant Aggregation no. Ref 100-
A. Alkyl sulfates (RSO,-M+)
R = n-C. M = Na 20 24
n-c, Na 31 25
n-C., Na 36:42:50 25:11:26
$60-
n-C;: Na 40141157;62;70;80 27;11128;29;26;30 z
n-c,, Li 6 3 29
B. Alkyl sulfonates (RSO,-M+)
R = n-C, M = N a 24 26
n-C,, Na 4 1 26 20 -
n-C,, Na 45;54 11;26
n-C,, Na 70;80 11;26 I 1 I I I I I
7 9 11 13 15 17
C. Alkyl trimethylammonium bromides (RNMe,Br)
R = n-C, 23 31 nC

n-C, 30 31 Figure 7. Aggregation numbers (Table 11) as a function of n,; solid


n-c,, 36;44 23;31 line is Nagg
calculated as described in text.
n-c12 40;50;50;62 11 ;23;26;31
n-c14 75;92 23;31
80;95 11;32 TABLE 111: Calculated Surface Area per Monomer
n-CI6
D. N-Alkylpyridinium bromides (R-Pyr’Br-) nC NacSa Core surface Head groupb
R = n-C, 24 31 8 23 66.16 78.72
n-c,, 42 31 9 30 64.94 75.79
n-c,, 58 33 10 36 65.11 74.99
n-c,, 79 31 11 42 63.44 74.69
n-c16 87 11 12 40 70.25 79.96
14 75 62.67 69.32
(solvent interpenetration volume) can be described as a 16 80 66.67 73.30
function of the number of monomers capable of existing a Lowest Nagsfor a particular n, for series C and D
in the reduced core by from Table 11. Assumed 1.0 A beyond core surface.

(9) the scattering technique developed by Debye.7J3v23This


technique has been applied to a number of micellar sys-
tems and some of the pertinent results are collected in
Table I1 for systems at (or near) the cmc in pure water,
Le., in the absence of supporting electrolyte. The errors
void -
- AI’- ~2 associated with the determination of Nagghave been
monomer Nn,-2 discussed1’ and the higher values of Nagg reported for a
particular surfactant can generally be disregarded.l’ The
where AV is the volume difference between a sphere n, aggregation numbers from Table I1 are presented in Figure
atoms in radius and a sphere n, - 2 atoms in radius, u2 is 7 relative to the curve of N,,, calculated for spherical
the total volume of two-carbon “fragments” beyond the models employing n, for the calculation of 1 (eq 2). Most
core, and N,,-z is the aggregation number of the sphere of of these experimentally determined aggregation numbers
reduced core. For n, - 2, the void volume decreases by are less, within experimental error,” than N,,, for a
20% from n, = 7 to n, = 16, indicating that the two particular n,. Granted that these micelles possess spherical
carbons most proximate to the head group of the hexadecyl geometry, as has been suggested by others18,11J2the chain
system are 20% less solvated than the corresponding two truncation procedure employed by Tanfordlo suggests
atoms in the heptyl system. On the other hand, if the total premature changes from spherical to nonspherical ge-
chain length is employed to calculate N,,, the surface area ometry.
per monomer a t the core-solvent interface is, for all Aggregates containing less than N,,, monomers are
practical purposes, invariant (Figure 3). If minimization acceptable entities. A priori, it should not be expected that
of the hydrocarbon-solvent interface is a major driving aggregation numbers should necessarily equal N,, due to
force for micellization, all n, atoms should occupy the core the extremely wide range of surface area per head group
and solvent should be maximally excluded, a conclusion at reasonable distance increments from the core surface.
previously reached by Stigter.17 Calculation of the surface area per monomer for the lower
Calculation of N,,, based on truncated chain lengths aggregation numbers presented in Table I1 shows that the
may actually underestimate the aggregation numbers of average surface area per monomer (assuming spherical
micelles. If it is assumed that 1 (calculated from n,) is an geometry) at the core surface for all C8to C16surfactants
average value and that the micellar surface is irregular22 (in Table 11) is 65.6 f 4.6 A2 (Table 111),within experi-
(rough) then some volume is still allowed for solvent mental error of that calculated above (Figure 3) for
penetration and N,, (based on n,) becomes a reasonable spherical micelles. Assuming a core free of solvent, the
estimate for the aggregation number. We have therefore radius required for the requisite volume of hydrocarbon
chosen to roughly estimate core volumes (and aggregation can be calculated. If the head groups are assumedI7to lie
numbers) on the basis of the maximum extended chain 1.0 A beyond the core surface for the trimethylammonium
length of a monomer. and pyridinium compounds in Table 11, the surface area
per head group is found to be 75.3 f 5.9 A.2 This narrow
Discussion range is indicative of similar, if not identical, head group
The most widely employed method for determining the interactions as might be expected within a homologous
size (aggregation number (Nagg))
and shape of micelles is series. If the surface area per monomer at the head group
The Journal of Physical Chemlstty, Vol. 8 1, NO. 2, 1977
134 J. E. Leibner and J. Jacobus

100

‘4
- 8 12
“C
16 20

Flgure 8. Aggregation numbers (Table 11) as a function of


tine is Nagg as a function of n, for I - 0.6 A.
n,; solid
8 12 16 20
nC

were constant, it would be expected that the fraction of Flgure 9. Surface area/monomer at I - 0.6 and at I + 0.6 A.
charge should, within a homologous series, be invariant.
The calculation of radii of spherical cores from aggre- per monomer at the core surface may, depending on the
gation numbers less than N,, (ammonium and pyridinium electrostatic demands of a particular head group, vary from
compounds in Table 11) reveals that these radii are, in this value.
general, ca. 0.6 8, less than 1 calculated from n, (eq 2). As surfactant concentrations are increased beyond the
Radii of length less than 1 are reasonable if conformational cmc, numerous micellar systems display increased ag-
mobility is considered for the hydrocarbon tails. Spec- gregation numbers, e.g., hexadecyltrimethylammonium
troscopic indicate chain mobility remote from bromide (CTAB) exhibits a large increase in micelle
the polar head groups. In order to occupy the total volume molecular weight.32p34,35 A similar increase in aggregation
of the reduced core extensive chain “crimping” must occur, number is observed for many systems upon addition of
Le., the chains cannot be arranged in a radial fashion away common gegenion, e.g., CTAB, spherical at the cmc,
from the center of the core nor can they exist exclusively displays a markedly increased aggregation number upon
in the anti conformation. Whether or not this dimensional addition of KBr (Nagg ca. 2000 and 5000 in the presence
reduction is real, or an artifact of these calculations, is of 0.178 and 0.233 M KBr, respectively; co = 2.72 X
unclear. The dimension in question could actually be M).13 Sodium dodecyl sulfate (SDS), a particularly
greater than that calculated above; such would be the case well-characterized system,%displays increased aggregation
if extensive solvent penetration occurs to occupy the number in the presence of NaC1.27i29~36
unfilled volume so produced. Counterion binding studies37employing 81Br nuclear
Calculation of maximum aggregation numbers for magnetic resonance spectroscopy indicates that as CTAB
spheres of radius 0.6 8, less than 1 calculated from eq 2 concentrations are increased (no supporting electrolyte)
yields resulting values (Figure 8) remarkably close to those enhanced bromide binding (to a rod shaped micelle)32*34,35
experimentally determined for the alkyltrimethyl- is observed. Such enhanced binding would be predicted
ammonium and alkylpyridinium bromides listed in Table for any model which displays decreasing surface area as
11. The surface area per monomer at the core surface a function of aggregation number. It is readily shown that
(radius = 1 - 0.6 A) and at the polar head groups (radius at constant volume the coalescence of n spheres (or n
= 1 + 0.6 8,;the C-N bond is ca. 1.5 8,) are graphically cylinders) to a (larger) cylinder results in a loss of surface
depicted in Figure 9. For n, in the range 8-16, the average area of
surface area per monomer at the core is 65.41 f 0.62 A2, 4
while at the head groups it is 76.15 f 5.05 A2. Thus, with ASA = (1 - n)-n12 (12)
all carbon atoms considered in the core, the water- 3
hydrocarbon surface area per monomer is invariant, but where 1 = micelle chain length. This loss of surface area
head group solvation (void volume) is greater for short must be compensated for by increased gegenion binding
chain amphiphiles than for long chain amphiphiles. The (to minimize electrostatic interactions). I t is interesting
wider separation of head groups for small n, implies that to note that at high concentrations potassium salts of
the fraction of charge should decrease with increasing chain n-alkanoic acids (in the cylindrical (M1)38phase) possess
length of monomer. Unfortunately, data of sufficient surface areas per polar head group of 47-57 A2, values
degree of accuracy are unavailable to test this prediction closely approximated by consideration of the change in
for the compounds discussed above. However, we believe surface area as Nagg becomes large (Figure 6).39
that the aggregation numbers presented in Figure 8 should Determinations of micelle shapes above the cmc and/or
be regarded as predictions for studies involving the de- in the presence of added common gegenion have indicated
termination of aggregation numbers at the cmc in pure the presence of rod-shaped micelles.13~15~32~34~35~40To our
water of alkyltrimethylammonium bromides and alkyl- knowledge, charged micelles have never been unequivocally
pyridinium bromides. These calculations are not meant demonstrated to exist as oblate ellipsoidal aggregates.
to imply that all spherical micelles will assume core vol- Debye and Anacker13 and Reiss-Husson and Luzzati15
umes consistent with surface areas per monomer (at the have, to the contrary, ruled out the existence of oblate
core surface) of ca. 66 A2. For the systems listed in Table ellipsoidal aggregates for a number of the more common
I1 this is apparently the case, but the actual surface area charged micelles. Transition from a spherical micelle with
The Journal of Physical Chemistry, Vol. 81, No. 2, 1977
Charged Micelle Shape and Size 135

greater surface area per monomer at the head group to a to uncharged (or zwitterionic) surfactants, the micellization
cylindrical micelle with reduced surface area per monomer of which are assuredly controlled by hydrophobic inter-
at the head group requires either increased monomer actions, but whose head group interactions are not strictly
concentration or addition of common gegenion, both comparable to charged systems.
circumstances are manifest as higher ionic strength, to
balance the expected increase in repulsive electrostatic Acknowledgment. This work was supported by Grant
interactions. We believe that the calculations presented No. 1-R01-GM22788-01from the NIGMS, U.S.Public
herein indicate that the most likely transition observed Health Service. We thank Professor Janos Fendler,
during increasing aggregation is from sphere to hemisphere Professor Gary Powell, and Dr. Dirk Stigter for their
capped cylinder, without the intermediacy of ellipsoidal cogent comments on this work.
(oblate or prolate) geometrie~.~’ References and Notes
If increased aggregation (beyond N,,,) with retention See, for example, the critical review of micellization by P. Mukerjee
of spherical geometry were to occur, successively more of and K. J. Mysels, NatL Stand Ref Data Ser., NatL Bur. Stand., No.
the constituent monomer hydrocarbon chains would be 36 (1971).
forced to be exposed to solvent, i.e., the hydrocarbon-water Thii work has recentJy been reviewed (J. H. Fendler and E. J. Fendler,
“Cataiysisin Micellar and Macromdecuhr Systems”, Academic Press,
interface would increase. Since such an increase is en- New York, N.Y., 1975).
ergetically prohibitive, it should not be expected to occur. G. S. Hartley, “Aqueous Solutions of ParaffinChain Salts”, Hermann
Rather, due to increasing ionic strength, a reduction of et Cie, Paris, 1936.
J. W. McBain, “Colloid Chemistry”, Vol. 5,Reinhold, New York, N.Y.,
surface area per head group should be favored and a 1944.
smooth transition from spherical to cylindrical geometry W. D. Harkins, J. Cbem. Pbys., 16, 156 (1948).
should result. M. L. Corrin, J. Cbem. Pbys., 16, 844 (1948).
P. Debye, Ann. N. Y. Acad. Sci, 51, 575 (1949).
Although cylindrically shaped micelles are preferred A. D. Abbot and H. V. Tartar, J. Pbys. Cbem., 59, 1195 (1955).
above the cmc of most amphiphile~,’~,~~ the production of H. Schott, J. Pbarm. Sci., 60, 1594 (1971).
bilayers is possible if the surface area per monomer is (a) C. Tanford, J mys. Cbem, 76, 3020 (1972); (b) C. Tanford, “The
sufficiently reduced. For single chain amphiphiles the Hydrophobic Effect: Formation of Micelles and Bo!ogIicalMembranes”,
Wiley, New York, N.Y., 1973.
calculated surface area reduction is drastic (to ca. 21 A2 H. V. Tartar, J. Colloid Sci, 14, 115 (1959).
per head group). Experimentally, bilayers (lamellar (G)38 G. Zografi and S. H. Yalkowsky, J. Pbarm. Sci., 61, 651 (1972).
phases) have been observed in concentrated solutions of P. Debye and E. W. Anacker, J Pbys. ColIoidCbem., 55, 644 (1951).
D. Stigter, J. Colloid Interface Sci, 47, 473 (1974).
the potassium (and other) salts of n-alkanoic acids which F. Reiss-Husson and V. Luzzati, J. Pbys. Cbem., 68, 3504 (1964).
exhibit surface area per head group of ca. 32-38 A2,39close D. Stigter, J. Pbys. Cbem., 70, 1323 (1966).
to the range calculated for amphiphiles possessing two D. Stigter, J. Pbys. Cbem., 78, 2480 (1974).
K. Kalyanasundaram and J. K. Thomas, J. Pbys. Cbem., 80, 1462
chains (Table I). This large discrepancy between calcu- (1976).
lated and experimental surface areas demonstrates the E. Williams, B, Sears, A. Allerhand, and E. H. Cordes, J. Am. Cbem.
inadequacy of any model which ignores specific head group Soc., 95, 4871 (1973).
R. T. Roberts and C. Chachaty, Cbem. Pbys. Lett., 22, 348 (1973).
interactions. K. Kalyanasundaram, M. Gratzel, and J. K. Thomas, J. Am. Cbem.
Soc., 97, 3915 (1975).
Conclusions D. Stigter and K. J. Mysels, J. Pbys. Cbem., 59, 45 (1955).
The models presented here have been\concerned with P.Debye, J. Pbys. Colloid Cbem., 53, 1 (1947).
the geometry of micelles. The sizes discussed for spherical E. Hutchinson and J. C. Melrose, Z Pbys. Cbem (Frankfurtam k i n ) ,
2, 363 (1954).
micelles represent most probable aggregation numbers, but W. Prins and J. J. Hermans, K Ned Akad Weterscbap., Ser. € 59,
I,
a limited range of sizes is not ruled out. The actual size 298 (1955).
of a micelle, either spherical or cylindrical, will intimately H. V. Tartar and A. L. M. Lelona, J. Pbys. Cbem., 59, 1185 (1955).
L. M. Kushner and W. D. HubbGrd, J. Colloid Sci, 10, 428 (1955).
depend on a variety of conditions, e.g., concentration, F. Reiss-Husson and V. Luzzati, J. Colloid Interface Sci., 21, 534
supporting electrolyte, polar head group, gegenion, tem- (1966).
perature, etc. Further, the models are based on the K. J. Mysels and L. Princen, J. Pbys. Cbem., 63, 1696 (1959).
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The Journal of Physical Chemistv, Vol. 81, No. 2, 1977