Jacobus
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.
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 (“DebyeAnacker 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
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
100
‘4
 8 12
“C
16 20
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 wellcharacterized 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 CN 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 816, 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 nalkanoic acids (in the cylindrical (M1)38phase) possess
length of monomer. Unfortunately, data of sufficient surface areas per polar head group of 4757 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 rodshaped 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 ReissHusson 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. 1R01GM2278801from 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 hydrocarbonwater 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 nalkanoic acids which F. ReissHusson and V. Luzzati, J. Pbys. Cbem., 68, 3504 (1964).
exhibit surface area per head group of ca. 3238 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. ReissHusson 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).
J. N. Phillips and K. J. Mysels, J Phys. Cbem., 59, 325 (1955).
simplifying assumption that a major contributing factor H. J. L. Trap and J. J. Hermans, K. Ned. Akad Wetenscbap., Ser.
to micelle shape (and size) is the surface area per head B, 58, 97 (1955).
group (as a qualitative substitute for the electrical free P. Ekwall, L. Mandell, and P. Solyom, J Colloid Interface Scl., 35,
519 (1971).
energy) and have ignored the possibility that the con W. P. J. Ford, R. H. Ottewill, and H. C. Parreira, J. Colloid Interface
figurational chain entropy might be a dominant factor in Sci., 21, 522 (1966).
the determination of micelle shape and size. Thus, the K. G. Gotz and K. Heckmann, J. Colloid Sci, 13, 266 (1958).
models presented are of limited utility in a predictive sense; E. Graber, J. Lang, and R. Zana, Kolb@Z Z Pokm, 238,470 (1970).
E. W. Anacker, R. M. Rush, and J. S. Johnson, J. Pbys. Cbem., 68,
the ab initio calculation of aggregation numbers and critical 81 (1964).
micelle concentrations must await further improvement G. Lindblom, B. Lindman. and L. Mandell, J. Colloid Inferface Sci.,
of our understanding of the various factors affecting 42, 400 (1973).
P. A. Windsor, Cbem. Rev., 68, 1 (1968).
micellization. Attempts in this direction have recently B. Gallot and A. Skoulios, Kollol&Z Z Polym., 208, 37 (1966).
been ~ n d e r t a k e n . ~ ~ N. A. Mazer, G. B. Benedek, and M. C. Carey, J. Pbys. Cbem., 80,
We should like to emphasize that our remarks pertain 1075 (1976).
C. A. J. Hoeve and G. C. Benson, J. Pbys. Cbem., 61, 1149 (1957).
exclusively to charged micelles. A priori, there is no reason E. Ruckenstein and R. Nagarajav, J Pbys. Cbem., 79, 2622 (1975);
to believe that the models discussed here are applicable J. Colloid Interface Sci,, 57, 388 (1976).