744 J. Phys. Chem.

1980, 84, 744-751

(4) Funasaki, N.; Hada, S. J . Ph,ys. Chem. 1979, 83, 2471, and ref-
erences cited therein.
(5) Mukerjee, P.; Mysels, K. J. ACS Symp. Ser. 1975, No. 9 , 239.
(6) Mukerjee, P.; Yang, A. Y. S. J. Phys. Chem. 1976, 80, 1388.
(7) Funasaki, N.; Hada, S. Chem. Lett. 1979, 717.
(8) Hildebrand, J. H.; Scott, R. L. "The Solubility of Nonelectrotytes"; Dover
Publications: New York, 1964; Chapters 7 and 16 and Appendixes
1 and 4.
(9) Pagano, R. E.; Gershfeld, N. L. J. Phys. Chem. 1972, 76, 1238.
(10) The chemical structure of NF is
(CFa 12 C F\
(CF3)zCF
c,=c' \",Lo_,
-
0 ,No
(11) Funasaki, N.; Hada, S. Bull. Chem. SOC.Jpn. 1976, 49, 2899.
(12) MatijeviE, E.; Pethica, B. A. Trans. Faraday SOC.1958, 54, 1382.
(13) Mysels, K. J. J . Colloid Interface Sci. 1978, 66, 331.
(14) Shinoda, K.; Soda, T. J. Phys. Chem. 1963, 67, 2072.
(15) Tanford, C. J . Phys. Chem. 1972, 76, 3020.
(16) R. L. Scott, J . Am. Chem. SOC. 1948, 70, 4090.
(17) Hildebrand, J. H.; Fisher, B. B.; Benesi, H. A. J . Am. Chem. SOC.
1950, 72, 4348. Jolley, J. E.; Hildebrand, J. H. J. Phys. Chem. 1957,
61, 791. Shinoda, K.;Hildebrand, J. H. IbM. 1958, 62, 481; 1961,
65, 1885.
(18) Funasaki, N.; Hada, S., unpublished results.
(19) Menger, F. M.; Jerkunica, J. M.; Johnston, J. C. J . Am. Chem. SOC.
1978, 700,4676. Muller, N.; Birkhahn, J. H. J . Phys. Chem. 1967,
77, 957. SvenS, B.; Rosenholm, B. J. ColloidInterfacs Sci. 1973,
44, 495. Corkill, J. M.; Goodman, J. F.; Walker, T. Trans. Faraday
SOC.1967, 63, 768. Clifford, J. Ibid. 1965, 67,1276.
(20) Menger, F. M. J. Phys. Chem. 1979, 83, 893. Acc. Chem. Res.
1979, 72, 111.
(21) Mukerjee, P. J. Colloid Sci. 1964, 79, 722.
(22) Overbeek, J. Th. G.; Stigter, D. Recl. Trav. Chim. Pays-Bas 1956,
75,1263. Mukerjee, P. Adv. ColloldInterface Sci. 1967, 7, 241.
Anacker, E. W. In "Cationic Surfactants"; Jungermnn, E., Ed.; Marcel
Dekker: New York, 1970; p 203. Tanford, C. "The Hydrophobic
Effect: Formation of Micelles and Biologlcal Membranes"; Wiley-
Interscience: New York, 1973; p 45.
(23) Hall, D. G.; Pethica, B. A. In "Nonionic Surfactants"; Shick, M. J.,
Ed.; Marcel Dekker: New York, 1967; p 516.
(24) Hill, T. L. "Thermodynamics of Small Systems"; W. A. Benjamin: New
York, 1963-1964; Vol. 1 and 2.
(25) Mukerjee, P. Kolloid Z. 2. Polym. 1970, 236, 76.
(26) Metheson, I. B. C.; King, A. D., Jr. J . Colloid Interface Sci. 1978,
66,464.
(27) Goodrich, F. C. "Proc. Int. Congr. Surf. Act., 2nd, 79571957, 7,
85. Defay, R.; Prigogine, I.; Bellemans, A,; Everett, D. H. "Surface
Tension and Adsorption"; Longmans: London, 1966; Chapter 12.
Lucassen-Reynders, E. H. J . Colloid Interface Sci. 1973, 42, 563.
Nakagaki, M.; Funasaki, N. Bull. Chem. SOC.Jpn. 1974, 48, 2094,
2482. Funasaki, N.; Nakagaki, M. Ibid. 1975, 48, 2727. Goddard,
E. D. Adv. Chem. Ser. 1975, No. 744, Chapters 3, 12, and 13.
Gershfeld, N. L. Annu. Rev. Phys. Chem. 1976, 27, 349. Motomura,
K.; Yoshino, S.; Fujii, K. Matsuura, R. J. Collokl Interface Sci. 1977,
60, 87. Garrett, P. R. Ibid. 1977, 62, 272.
(28) Stigter, D. J . Phys. Chem. 1975, 79, 1008; 1964, 68, 3603. Fgat,
G. R.; Levine, S. Adv. Chem. Ser. 1975, No. 744, Chapter 8.

Micelle Size and Shape of Sodium Dodecyl Sulfate in Concentrated NaCl Solutions

Shoji Hayashi and Sholchi Ikeda"

Department of Chemistry, Faculty of Science, Nagoya University, Chikusa, Nagoya 464, Japan (Recelved April 2, 1979;
Revised Manuscript Received December 12, 7979)

Light scattering from aqueous solutions of sodium dodecyl sulfate has been measured in the presence of NaCl
of different concentrations at different temperatures. In NaCl solutions more concentrated than 0.45 M, surfactant
micelles fbrmed at the critical micelle concentration further associate into large micelles with increasing surfactant
concentration. In 0.60 and 0.80 M NaCl at 25 "C, light scattering exhibits anomalous dissymmetry attributable
to the formation of trace amounts of microgel particles. In 0.80 M NaCl at 35 "C, light scattering is normal
and gives the micelle aggregation number as high as 1410 at 1.10 X g ~ m - The
~ . angular dependence indicates
formation of a rodlike micelle having a length of 597 A. It is concluded that sodium dodecyl sulfate forms spherical
micelles at low NaCl concentrations (10.45 M), but it associates into rodlike micelles at high NaCl concentrations
when its micelle concentration is high.

Introduction
Recently Mazer, Benedek, and Carey1 measured qua-
sielastic light scattering from aqueous solutions of sodium
dodecyl sulfate (SDS) in the presence of NaCl of different
concentrations and found that the micelle aggregation
number increases from about 80 in 0.15 M NaCl to about
1000 in 0.6 M NaCl a t 25 "C. The small micelle having
an aggregation number less than about 100 has been as-
sumed to be spherical or globular in ~ h a p e . ~However,
-~
the large micelle cannot be accommodated to a globular
micelle but has been assigned a rodlike shape.' The same
workers together with their co-workers6further observed
angular dependence of light scattering and confirmed the
formation of rodlike micelles.
Unfortunately it proved that the SDS samples they used
were not sufficiently pure but contained considerable
amounts of higher alkyl homologues.6 Furthermore, they
did not examine variation of light scattering and micelle
size with SDS concentration in detai1.l
These workers measured light scattering at various
temperatures from 11to 85 "C, but the temperatures in-
.OO/O
0022-3654/80/2084-0744$01
cluded the range that was considerably lower than the
temperature of solubility limit or the critical micelle tem-
perature of SDS in 0.6 M NaC1.' This fact could cast
suspicion if the SDS solutions that they studied and in
which they found the rodlike micelles were unstable and
contained small crystallites. The formation of rodlike
micelles first proposed by Debye and Anacker7i8has long
been accepted with serious reservation by other worker^.^#^
In the present work we have measured light scattering
from aqueous solutions of SDS in the presence of con-
centrated NaCl at different temperatures and examined
their behavior as a function of SDS concentration at tem-
peratures above and below its solubility limit. Conditions
for preparing and clarifying SDS solutions and for light-
scattering measurements have been carefully defined, and,
especially, the temperatures for all these stages have been
strictly regulated. A series of SDS solutions of concen-
~ ) been prepared by dissolving SDS
trations c (g ~ m - has
solid in an NaCl solution of a given concentration, C, (M).
We have found that a transition of micelle shape from
sphere to rod occurs in SDS solutions of concentrations
0 1980 American Chemical Society
Micelle Size arid Shape of Sodium Dodecyl Sulfate
well above the critical micelle concentration (cmc) when
the NaCl concentration is higher than 0.45 M. In the
temperature range below the solubility limit and even
above but not far from it, anomalous angular dependence
of light scattering has been observed with SDS solutions
containing medium amounts of micelles, and this has been
attributed to the formation of trace amounts of microgel
particles, possibly each composed of a network of spherical
micelles linked by some cations and occluding solvent, but
not to the presence of small crystallites.
Experimental Section
Materials, SDS was purchased from the Nakarai
Chemical Co., Inc., Kyoto, as the special reagent for protein
analysis, lot no. M7K6587. The reagent was extracted with
dry ethyl ether for 12 h on a Soxhlet extractor, and then
it was recrystallized from ethanol as follows. About 17 g
of the material was dissolved in 1 L of ethanol a t 70 "C,
and after filtration the solution was cooled to 18 "C. About
11g of SDS was collected. It was dried at 100 "C in vacuo
for 10 h and stored over P205.
The SDS sample was analyzed for dodecanol and dis-
tribution of lnydrocarbon chain length. It was extracted
with ethyl ether, and the ethereal solution was applied to
gas chromatography. It was found that the content of
dodecanol WEISless than 0.01%. The sample was refluxed
with 2 N H2S04for 2 h and then extracted with ethyl
ether. The ethereal solution was subjected to gas chro-
matography. The results showed that the sample consisted
of 0.24% Clo,98.10% CI2,and 1.66% CI4. The gas chro-
matographic analysis was performed on a Shimadzu 4BM
gas chromatograph using a Chromosorb W column at 120
"C.
Reagent grade NaCl (Tomita Chemical Co., Inc., To-
kushima) waR ignited on an evaporating dish for 1h and
stored in a desiccator until use. The amounts of divalent
cations in the NaCl were determined by atomic absorption
spectroscopy, and the reagent was found to contain 1.5
ppm of Ca and 1.0 ppm of Mg. Water was glass-redistilled
from alkaline KMn04.
A stock solution of SDS was prepared volumetrically by
dissolving a weighed amount of SDS solid into an NaCl
solution, either at room temperature (25 f 2 "C) or 35 f
0.01 "C, depending on whether the NaCl concentration was
less than 0.50 M or higher. After a day the stock solution
was diluted by the same NaCl solutions to prepare the
solutions for measurements. The SDS solutions in 0.60
and 0.80 M NaCl were kept at 35 f 0.01 "C for more than
overnight before clarification for light-scattering mea-
surements.
Solutions aitid solvents for light scattering were filtered
by a Sartorius membrane filter, SM 113, having a pore size
of 10 nrn, in an air bath kept at 36 f 1 "C. The filtration
was performed under pressure of about 2 atm, and the
filtrate was directly poured into the light-scattering cell
along its wall, About 10 cm3 of the filtrate was used to
rinse the cell, and the remaining 40 cm3 of filtrate was
filtered further three to four times, when it was dust-free.
For filtration of concentrated SDS solutions, close to 2 X
lom2g cmW3,in 0.80 M NaC1, however, it took about 3 h,
and they were, therefore, filtered only once.
Light Scattering. Light scattering was measured at 436
nm of a mercury lamp on a Shimadzu PG-21 light scat-
tering photometer with a constant temperature bath and
a small-slit system. A cylindrical cell was put in a tem-
perature bath made of brass similar to that of Tremen-
tozzi,1° througlh which water of constant temperature was
circulated from a Haake FS thermobath. The temperature
of solution or solvent was monitored by a dipped ther-
The Journal of Physical Chemistry, Vol. 84, No. 7, 1980 745
mistor tip and maintained constant within f0.05 "C.
The reduced intensity of light scattered in the angle 0
is calculated with eq 1,where Ioand IB are the intensities
sin 0 10
Rg =
+
1 cos2 6 lo
of incident and scattered light, respectively, measured by
the deflection of galvanometer and calibrated for the at-
tenuation by neutral filters, and 4 is the calibration con-
stant of the apparatus. The constant, 4,was determined
by measuring the light scattered from purified benzene at
25 and 30 "C, using the values Rw = 48.5 X and 49.5
X lo4 cm-l a t the respective temperaturell and taking
account of the refractive index of the solvent. The value
of 4 was found to be common a t the two temperatures
within 0.3%) and consequently it was assumed in the
present work that the calibration constant is unchanged
by temperature from 20 to 35 "C.
Refractive Index Increment. The refractive index in-
crement was measured on a Shimadzu DR-3 differential
refractometer of Brice type with a photoelectric attach-
ment. The apparatus was calibrated by aqueous solutions
of NaCl at 25 "C. The temperature was regulated within
fO.O1 "C by circulating water of constant temperature
around an oil bath and putting the cell therein. At least
four SDS solutions of the same NaCl concentration !were
measured against an NaCl solution of the same concen-
tration. Thus the increment, ( a f i / a c ) ~actually
~, measured
was Afi/c at constant temperature and NaCl concentration.
For solutions in 0-0.80 M NaCl a t 25 "C, it was found
that
(ace c,)= 0.121 - O.O22C,
For solutions in 0.80 M NaCl at 35 "C, the increment was
0.103.
Results
Figure 1shows the reduced intensity of light scattered
by aqueous SDS solutions in the presence of dilute NaCl
a t 25 "C. The dissymmetry of these solutions is 1.02 or
less. Although the curves are concave downward at 0.01
and 0.10 M NaC1, the curve turns concave upward at 0.50
M NaC1. All of them give linear Debye plots, but the plot
for 0.50 M NaCl has two sections having negative slopes,
as shown in Figure 2. The Debye equation is given by
(3)
where the subscript or superscript, zero, refers to the cmc,
K is the optical constant, M is the apparent micelle mo-
lecular weight, and B is the second virial coefficient.
Values of the apparent molecular weight, M , and the
apparent aggregation number, m' = M/288, of the micelle
are given in Table I, together with those of the cmc, co, and
the second virial coefficient, B. As can be seen in Figures
7 and 8, values of M are in harmony with those of Emerson
and Holtzer12and of Kuriyama,13but they are somewhat
higher than those of the o t h e r ~ . ~ J Recently
'>~~ Corti and
DegiorgiolGgave a value of M in 0.1 M NaCl in agreement
with ours.
The Debye equation does not take account of the effect
of micelle charge on light scattering, and the micelle mo-
lecular weight given by M is apparent in this respect. The
necessary correction for the charge effect can be made by
applying the equation of Prins-Hermans-Princen-My-
sels17Jsto obtain the micelle molecular weight, but the
results are valid only for an ideal charged micelle without
746 The Journal of Physical Chemistry, Vol. 84, No. 7, 1980 Hayashi and Ikeda

TABLE I: Micelle Characteristics of SDS in Low NaCl Solutions at 25 "C

____--
C.. M c,. g cm-3 M m' B, cm3 g-l M, m P P/m 4
0.01 0.15 X lo-' 20 200 70 5.89 x 10-3 22 100 76.7 12.7 0.17 1.10
0.10 0.042 X lo-' 27800 97 0.65 x 10-3 29100 101 15.1 0.15 1.05
0.50 0.013 X 42600 148 -0.085 X

10 -
9-

8 -

7-

--
I
E
6 -
u

In 5 -
I
0

-
r
4 -
0
m
3 -
1.6 1 1

I I , I I 1

0 0.2 0.4 0.6 0.8 1.0

c (10-2 g c m - 3 )
Figure 1. Reduced intensity, Reo,of SDS solutions at 25 "C and at
the following NaCl concentrations: (0)
0.01, ( 0 )0.10, and (0)0.50
M.
mutual equilibrium between monomers and micelles.
Values of the micelle molecular weight, M,, the aggrega-
tion number, m = Mm/288, and the micelle charge, p ,
obtained by this theory are also given in Table I.
In more concentrated (20.5 M) NaCl solutions, SDS
tends to cease to be soluble at 25 "C. The temperature
of solubility limit was termed the critical micelle tem-
perature,l which was determined as the midpoint of the
temperature range of dissolution of SDS when solid SDS
was shaken and warmed with aqueous NaCl solution. The
temperature is reported to be 24.7 "C in 0.50 M NaCl and
25.4 "C in 0.60 M NaC1, as shown in Figure 3, and it is
almost independent of SDS concentration. In our ex-
periments aqueous solutions of SDS were filtered at 36 f
1 "C and brought to temperatures for light-scattering
measurement successively by cooling, each time after a
series of measurements. We could keep the solutions clear
down to a temperature several degrees lower than the
critrical micelle temperature. Mazer and his co-workers1B6
measured light scattering of solutions even at 18 "C in 0.6
M NaC1. Undoubtedly these solutions must have been in
supercooled states, as they also noted. Such solutions are
suspected to contain crystallites portending imminent
pre~ipitation.~,~
Figure 2 shows reduced intensity, RW,and dissymmetry,
.z4 = R4/R13S, of SDS solutions in 0.60 M NaCl at different
temperatures. While the reduced intensity, RgO,smoothly
0 0.4 0.8 1.2 1.6 2.0
c ( 10-2 g cm-3 )
Figure 2. Reduced intensity, R,, and dissymmetry, q5,of SDS solutions
in 0.60 M NaCl and at the following temperatures: ( 0 )23, (0)
25, ( 0 )
27, and (0) 30 OC.
increases with increasing concentration, high dissymmetry
values are exhibited by solutions containing moderate
amounts of micelles at temperatures lower than 30 "C.
The dissymmetry is about 1.02 or less a t 30 "C. Similar
behavior of dissymmetry was observed for the solutions
in 0.50 M NaCl at temperatures lower than 25 "C. High
and anomalous dissymmetry was also associated with SDS
solutions in 0.80 M NaCl when the temperature was lower
than 35 "C. However, even at 35 "C the SDS solutions in
0.80 M NaCl showed dissymmetry around 1.1,but this was
found to be normal from the measurements of angular
dependence of light scattering, as shown later. The high
anomalous dissymmetry can be distinguished from the
normal dissymmetry by observing angular dependence of
scattered light, and it is seen that the anomaly comes
mainly from strong scattering a t low angles. This will be
discussed in more detail in the Discussion section.
In those solutions containing moderate amounts of
micelles and showing high anomalous dissymmetry, the
dissymmetry value increased with time even after the so-
lution reached the temperature of light-scattering mea-
surement. Nevertheless, it attained a steady value within
a few hours, which remained constant during the period
of measurement for about 3 h. In contrast, the reduced
Micelle Size and Shape of Sodium Dodecyl Sulfate The Journal of Physical Chemistry, Vol. 84, No. 7, 1980 747

TABLE 11: Micelle Characteristics of SDS in Concentrated NaCl Solutions

~~ ~~ ~

a t cmcap a t maximumC
I____

C,, hul temp, "C c,, g cm-? M m' M m'

--- ____I

0.501 25 0.013 X lo-' 42 600 3 48

30 0.014 X lo-' 39 300 136
0.60 25 0.012 x (50 OOQ) (1 74) 152 000 528
30 0.013 X low2 (43 500) (151) 111000 385
0.80 25 0.011 x 470 000 1630
30 0.012 x 352 000 1220
35 0.013 X 262 000 909
a Equation 3, or eq 5 and 4 with B ~2 0. Values in parentheses obtained by smooth extrapolation to the cmc. Equa-
tions 5 and 4 with B = 0.

-
I I I Y)
I0

0 .
d

2 IB
Y I I I I I I

0 0.2 0.4 0.6 0.8 1.0

h
*
O
"
24
d Nevertheless, we could keep the SDS solutions free from
E
c 20
I "
0 0.2 0.4 0.6 0.8
Figure 3. Relaticins of temperature for anomalous dissymmetry and
critical micelle temperature with NaCl concentration. Ovals indicate
points where light scattering was measured. Values circumscribed are
the largest values of dissymmetry, and values underneath are the SDS
concentrations (X lo-' g cm3) where they were observed: (-) threshold
curve for normal and anomalous dissymmetries, (- -) critical micelle
temperature defined by Mazer et al.,' and its extension.
(-.a)
intensity, RN,did not show such a perceptible change with
time. In view of its normal behavior with respect to SDS
concentration and temperature, as seen in Figure 2, the
value of RgOitself would be free from the anomaly and
could be considered to reflect the micelle characteristics.
The anomalous dissymmetry decreases as the SDS con-
centration increases beyond some value, and it becomes
difficult to distinguish the anomalous behavior from the
normal one, foir example, in 2 X g cm-3 SDS solution
in 0.60 M N a C l at 25 "C, which Mazer and his co-workers'
investigated in detail.
Figure 3 shows the relations of the temperature of
anomalous disaiymmetry and the critical micelle temper-
ature with NaCl concentration. The threshold curve be-
tween normal and anomalous behavior can be drawn rather
clearly, and it is seen to differ from the curve for solubility
limit. The anomalous behavior appears even a t temper-
atures higher than the critical micelle temperature.
(c-co) ( 1 0 - 2 g cm-3
Flgure 4. Debye lots for SDS solutlons In 0.50 M NaCl at the following
temperatures: (6)25 and (a)30 OC.
precipitation even at temperatures several degrees lower
than the critical micelle temperature. That is, the SDS
solution can be readily supercooled and retained in the
metastable state for a sufficiently long time, even in the
presence of concentrated NaC1.
Figure 4 shows the Debye plots of SDS solutions in 0.50
M NaCl at 25 and 30 "C, for which the dissymmetry is less
than 1.02. The micelles formed at the cmc gradually as-
sociate into larger micelles with increasing micelle con-
centration. Table 11gives values of the apparent molecular
weight, M , of the micelle at the cmc as well as those of the
cmc.
Each Debye plot consists of two linear ~ e c t i o nand
, ~ the
break cannot be eliminated by choosing any other cmc
value. Consequently, we may infer that the micelle growth
is further promoted by the increase in micelle concentra-
tion above a certain yalue. Such an observation can be
compared with the results of two groups of workers on SDS
solutions of almost equal NaCl concentration: Mysels and
Princen,14who worked a t low SDS concentrations, 0-0.5
X ~ , a weakly positive slope, B = 0.15 X
g ~ m - found
cm3 g-l, whereas Emerson and HoltzerI2 reported a
negative slope, B = -0.56 X cm3 g-l, a t the concen-
tration range (0.4--1.2) X g cm-3.
Figure 5 shows the Debye plots of SDS solutions in 0.60
and 0.80 M NaC1, for the scattering at 90a direction. In
0.60 M NaCl the solutions showed anomaly in dissymmetry
at temperatures lower than 30 "C, and in 0.80 M NaCl the
solution was normal only at 35 "6. However, even with
the solution showing high anomalous dissymmetry, the
value of reduced intensity at 90" angle, RgO,can be re-
garded as free from the anomaly and would stand for the
micelle characteristics if the internal interference could be
corrected. Then the Debye plots suggest that the micelles
formed at the cmc sharply associate into large micelles with
increasing micelle concentration. The observed micelle
748 The Journal of Physical Chemistry, Vol. 84, No. 7, 1980
2.5 I I I I
I I I I
0 0.5 1.0 1.5 2.0
( c -cg) ( 1 0 - 2 g cm-3
Flgure 5. Debye plots for SDS solutions in 0.60 and 0.80 M NaCI. Light
scattering at 90" direction. Upper: 0.60 M; (0)
25 OC, ((3) 30 'C.
Lower: 0.80 M; (0)
25 "C, (a)30 'C, (0) 35 'C.
growth and the formation of large micelles in concentrated
NaCl are in agreement with those found by other work-
erdJ6 in 0.6 M NaCl.
The small micelle has a molecular weight of 20000-
30 000, whereas the large micelle has a much larger size
characteristic of NaCl concentration, and it grows very
sensitively with increasing NaCl concentration.
Since the reduced intensity at 90' direction, Rw, would
not be influenced by the anomaly in dissymmetry, we
assume that an approximate molecular weight of micelle
is given by the value of M defined by eq 4,even when the
M = MwP(90) (4)
dissymmetry is anomalous. Here M , is the micelle mo-
lecular weight, P(90) is the value of particle scattering
factor at 90°, and the intermolecular interaction is assumed
to be negligible, Le., B = 0. Table I1 gives values of M at
the cmc and the largest value of M at n finite micelle
concentration in 0.60 and 0.80 M NaC1. The value of M
in eq 4 for concentrated NaCl solutions will be employed
together with that of M in eq 3 for low NaCl solutions in
the Discussion section, although the former is subject to
optical interferences.
The correct values of various micelle parameters can be
estimated by extrapolating the Debye plots to zero scat-
tering angle, unless angular dissymmetry is anomalous. In
such cases the light-scattering equation is given by
Here the particle scattering factor, P(@,is expanded in the
form
where X is the wavelength of light (436 nm), Ro the re-
fractive index of solvent, and RG the radius of gyration of
micelle. If the micelles are polydisperse, M , is their
weight-average molecular weight and RG is their some-
higher-order-average radius of gyration.
Hayashi and Ikeda
c-co
i 1 0 - 3 g cm-3)
1.7 0
3.53
5.36
18.2
11.0
3
0 0.2 0.4 0.6 0.8 1.0
sin24
L
Flgure 6. Angular dependence of light scattering from SDS solutions
in 0.80 M NaCl at 35 'C.
Since the size of a large micelle is defined by the NaCl
concentration, as can be seen from the curves in Figure
5 leveling off at high SDS concentrations, it is presumed
that the SDS solution contains, at least, two kinds of
micelle, i.e., the small spherical micelle formed at the cmc
and the large micelle, and that the latter fraction increases
with increasing SDS concentration. Thus the largest value
of M cited in Table I1 can be taken as the apparent mo-
lecular weight of the large micelle.
Figure 6 shows angular dependence of light scattering
from SDS solutions in 0.80 M NaCl at 35 "C. The inter-
cept of the curve gives the reciprocal of the weight-average
molecular weight, M,, of the micelle at a given micelle
concentration when B = 0 is assumed. Although the mi-
celle formed at the cmc would have a molecular weight of
about 50000, the apparent micelle molecular weight at 1.10
X IOv2g amounts to 284000, which cannot be ac-
commodated to a spherical micelle. The angular depen-
dence of light scattering shows the difference in micelle
size clearly, the limiting slope being zero at low micelle
concentrations but finite at high micelle concentrations.
The finite slope can be assigned to the large micelle, and
the contribution of the small micelle to the slope would
be negligible. The slope gives the radius of gyration, 172
A, at 1.10 X g ~ m - ~This
. corresponds to the length
of a rigid rod, L = 597 A, which can be fit well to the
apparent micelle molecular weight, 284000, or the apparent
micelle aggregation number, 986.
Apart from the possible dynamic character of the rodlike
micelle, as in the case of spherical micelles,lg we may derive
a more exact structure of the rodlike micelle, assuming a
rigid rod. In order to derive the exact value of the mo-
Micelle Size arid Shape of Sodium Dodecyl Sulfate
lecular weiglht of the rodlike micelle, we have to take ac-
count of the contribution of the second virial coefficient,
B, in a manner proposed by Prins and H e r m a n ~ and l~~~~
adapted by Pvhkerjee22for the multiple-step micellization.
Since the NaC1 concentration concerned is high enough
to suppress the electrostatic effect between charged mi-
celles, it is assumed that the second virial coefficient comes
from the excluded volume effect alone. For a solution of
rigid spheroicylindrical particles it is given by
4NA v m n
B=------- f (7)
MW2
where N A is Avogadro's number, V,, the volume of the
spherocylincler, and f its shape factor
P
f = l t
1 Z
Br(4r t1 )
r being the radius of the cylindrical part, and 1 its length.23
The length of the spherocylinder is equal to L = 1 t 2r,
when applied to the rodlike micelle. Assuming r = 20.5
A, using L = 597 A, and solving eq 5 for B = 0, we obtain
the micelle rr~olecularweight, M, = 405 000, or the micelle
aggregation number, mn = Mw/288 = 1410. The second
virial coefficient is then calculated to be 0.48 X cm3
g-l from eq 7 and 8.
Theee results lead to the molecular pitch of the rodlike
SDS micelle, Limn = 0.42 A. Assuming the crms-sectional
diameter of SDS molecule to be 6.7 A, the micelle should
contain about 16 molecules in its cross section, and thus
the rodlike micelle of SDS in 0.80 M NaCl at 35 "C consists
of a stack of 88 such disklike layers.
Discussion
We have shown that the rodlike micelles are formed in
SDS solutions at concentrations well above the cmc if the
NaCl concentxation is high, whereas the spherical micelles
are stable in dilute NaCl solutions. The transition of
micelle shape from sphere to rod is induced by a change
in NaCl concentration when the micelle concentration is
finite. Figure 7 shows the relation of the logarithm of
apparent micelle molecular weight, M , with the logarithm
of ionic strength, Co t C,, where Co is the cmc in molar
unit. It includes data of M at different temperatures for
high NaCl concentrations. Figure 7 indicates different
logarithmic relations for spherical and rodlike micelles. At
25 "C two linear relations intersect at the point of 0.45 M
NaC1, and M = 33 100 or m' = 115. The linear relations
can be represented by eq 9a and 9b. Below 0.45 M the
log M := 0.118 log (C, t C,) + 4.54 C, I 0.45 (9a)
log M E- 4.68 log (C, + C,) t 6.15 C, 1 0.45 (9b)
micelle size can be fit to the spherical or globular micelle,
whereas above 0.45 M it has to be assigned the rodlike
shape, as can be imagined from the results derived in 0.80
M NaCl a t 35 "C. It is seen that the data of Emerson and
Holtzer12 also fit eq 9a.
In a previous paper20we have shown that similar loga-
rithmic relations of apparent micelle molecular weight with
ionic strength hold for a series of some cationic surfactants
in NaCl solutions. If one compares the coefficients of eq
9, 0.118 and 4.68, with those for dodecyldimethyl-
ammonium chloride, 0.105 ahd 2.64, it is seen that rodlike
micelles of SDS increase their size about 1.8 times more
sharply than those of dodecyldimethylammonium chloride
as the ionic strength is increased. This would be caused
by different degrees of counterion binding on rodlike
The Journal of Physical Chemistry, Vol. 84, No. 7, 1980 749
-2 -1.5 -1 -0.5 0
log( C O * C S )
Flgure 7. Logarithmic relation of apparent micelle molecular weight
(0
with ionic strength: and -) 25 O C ; (A) 30 O C ; (e)35 "C;(0)data
of Emerson and Holtzer.'*
micelles between the two surfactants. Such a difference
could be revealed in their solubility behavior a t 25 "C:
SDS is soluble only in low NaCl solutions, but dodecyl-
dimethylammonium chloride dissolves in NaCl solut,ions
concentrated as high as 4.00 M.
From the above results it can be presumed that the
micelle formation of SDS in concentrated NaCl solutions
occurs in two steps when the SDS concentration irJ in-
creased. The steps can be represented by eq 10a and lob,
mD G D, (loa)
nD, G D,, (Lob)
where D is the monomer, D, the spherical micelle, and D,
the rodlike micelle. The molecular weights of spherical
and rodlike micelles are determined by NaCl concentrakion
and temperature, and the molecular weight derived from
light scattering at an SDS concentration represents the
weight-average molecular weight of the two kinds of mi-
celle, as was already noted above.
Next we will see the effect of temperature on micelle size
of SDS. Figure 8 shows the relation of apparent micelle
molecular weight with temperature a t different NaC1
concentrations. The value of micelle molecular weight in
0.10 M NaCl is consistent with that of Kuriyamaf3 and of
Corti and Digiorgio.16 Generally, the micelle size decreases
with the rise of temperature. This trend is in accord with
that found for ionic s u r f a c t a n t ~ and
~ ~ is
J ~in~contrast
~~~~~
with that for nonionic surfactant^.^^,^^^^ It is noticed that
the rodlike micelle formed a t high NaCl concentrations
decreases its size about 5 times more sharply than the
spherical micelle as the temperature is raised.
Finally we will discuss the nature of anomalous dissym-
metry of light scattering. Figure 9 illustrates the angular
dependence of scattered light for SDS solutions in 0.60 M
NaCl at 25 "C, for which anomalous dissymmetry is ob-
served a t low micelle concentrations. Just above the cmc,
where the dissymmetry is the largest, the curvature of the
scattering curve is very large and concave downward at low
75Q The Journal of Physical Chemistry, Vol. 84, No. 7, 1980 Hayashl and Ikeda

6.0 I I I I aqueous solution^,^^-^^ and such behavior has been at-

tributed to the presence of trace amounts of microgel
Furthermore, anomalous angular de-
pendence of light scattering has often been observed during
the course of either association or dissociation of polymers
after dissolved in s o l ~ t i o n . " ~ ~Linear
~ ~ ~ ' polymers them-
selves cannot form microgels but associate into crystalline
5.5 bundles of linear chain^.^^"^ However, cross-linking be-
tween linear or branched polymers would lead to such
microgel particles consisting of polymer network and oc-
cluded solvent.
Although SDS is soluble in 0.60 and 0.80 M NaCl and
the solutions are stable at 35 "C, lowering of temperature
5.0 induces the association of spherical micelles. Before
transforming into rodlike micelles, however, some of the
spherical micelles associate into other types of aggregates,
- 111
c9 Le., microgels, which would be metastable. The presence
of such a bypass could be facilitated by the following two
facts: (1)SDS has a high Krafft point and high critical
micelle temperatures, so that its micelle is unstable in
4.5 concentrated NaCl solution, and (2) an SDS molecule has
a large polar head group, so that it can accommodate to
a spherical micelle more favorably.20 Thus the spherical
Q-
micelles would tend to link with one another to form
microgel particles, possibly by some interaction of their
charged groups through cations. However, the amount of
I I I I
microgel particles is so small that the reduced intensity,
4.0 RBO,may not be influenced by their presence.3g
15 20 25 30 35 40 It is known that the reduced intensity as well as the
T e m p . C°C) dissymmetry of the solutions of impure SDS containing
Figure 8. Relatl,on of logarithm of apparent micelle molecular weight
0.1% dodecanol shows large increases just below the
with temperature at different NaCl concentratlons: (0)0.01, ( 0 )0.10, cmc,21~40~41However, in the present SDS sample no do-
(a)0.50, (0)
0.60, and ( 0 )0.80 MI (A)data of Kuriyama13 at 0.10 decanol was detected, but the anomaly was observed for
M, dissymmetry only. Furthermore, the anomalous dissym-
metry occurred only when the micelles were present and
also when the NaCl concentration was higher than 0.45 M
at 25 "C. These are not necessarily amenable to the sus-
pected contamination of SDS with dodecanol either. Some
amounts of higher alkyl homologues in the SDS sample
cannot be responsible for the anomalous dissymmetry,

I- since it disappeared at higher temperatures or a t lower

NaCl concentrations.
It seems more likely that some contaminant divalent
cations in NaCl link the negatively charged spherical
micelles to form a network. Such effects can be readily

-
reduced by increasing SDS concentration or raising tem-
perature, in accord with the observed results. The results
of trace analysis of metals in the NaCl used revealed
contamination of only trace amounts of various divalent
F metals, but it is also likely that trace amounts of contam-
inant cations are sufficient to link small amounts of
0.5 t -I spherical micelles present around tho crnc to form microgel
particles. The effect of such trace amounts of contaminant
0 0.2 0.4 0.6 0.8 1.0 could be made negligible or eliminated by the conversion
into rodlike micelles when the SDS concentration in-
sin28 creases.
2
Flgure 3. Angular dependence of light scattering from SDS solutions Acknowledgment. We thank Kenji Okahashi of the Kao
in 0.60 M NaCl at 25 O C and at the following SDS concentrations (XlO-' Soap Co., Inc., for gas chromatographic analyses of the
(0)
g ~ r n - ~ ) : 0.19, ( 0 )0.40, (0) 0.60, (131) 1.01, and (A) 2.01. SDS sample.
angles. With increasing concentration, the curvature be- References and Notes
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Electronic Structure of a Porphyrin Solid Film and Energy Transfer at the Interface with
a Metal Substrate

K, Tanlmura, T. Kawal, and T. Sakata"

Instltute for Molecular Science, MyodaJi, Okazakl444, Japan (Recelved February 5, 1979;
Revised Manuscrlpt Recelved August 6, 1979)
Publlcatlon costs asslsted by the Institute for Molecular Sclence

The electronic structure and the interaction with a metal substrate of amorphous solid films of free base
tetraphenylporphine (H,TPP) and its Zn derivative (ZnTPP) have been studied. The visible absorption spectra
resemble those of solutions, although the Soret band is greatly weakened and broadened in the film.The lifetime
of the SI state in an amorphous HzTPP film is less than 2 ne and is much shorter than that of solutions. This
quenching is attributed to enhancement of the nonradiative decay rate in the solid phase. The typical effect
of the metal substrate on the film is a strong quenching both of sensitized chlorin emission in ZnTPP and of
fluorescence in H2TPP. Forster type energy transfer to the metal substrate explains most of the quenching,
but an additional long-range effect in the H2TPP film is attributed to exciton diffusion within the film. The
metal-dye system is discussed in terms of a device for solar-energy conversion.

Introduction reported for porphyrin molecules in solutions as to their

Special attention has recently been attracted, because
of interest in solar-energy conversion mechanisms, to the
interesting phenomena exhibited by organic dyes at their
interface with other materials. A solid thin film of dye in
contact with mlids (metal, semiconductor, and insulators)
is one of the most common systems in which these inter-
facial phenomena have been ~ t u d i e d . l -Such
~ an organic
film plays a central role in the conversion of light into other
forms of energy through, in general, the following pro-
cesses: capture of photons and the transfer of the exci-
tation energy to the interfaces where carrier generation
and/or chemical reactions mainly take place. Thus,
clarification of excited-state behavior of dye film interfaces
with other solids, liquids, and gases is crucial for eluci-
dating the mechanisms of the various kinds of reactions
concerned, and hence for developing a system with high-
conversion efficiency. Nevertheless, detailed properties
of such excited states of dye films with interfaces are far
from being well understood.
In this paper, we study the electronic structure of the
porphyrin film and its interaction with a metal substrate.
The use of porphyrin (tetraphenylporphine and its metal
derivatives in this study) as an organic dye gives us several
advantages, since a great deal of data has already been
0022-3654/80/2084-0751$01 .OO/O
electronic structure, photochemical behavior, etcS8Prop-
erties of solid thin films of porphyrins are also interesting
as simple analogues to the chlorophyll aggregates in pho-
to~ynthesis.~J~
Experimental Section
Tetraphenylporphine (H,TPP) of chlorin-free grade and
the Zn derivative (ZnTPP) were obtained from Strem
Chemicals, Inc. and were used after recrystallization three
times from ethanol. Quartz plates polished to optical grade
and platinum (99.9%) plates were used as substrates after
cleaning their surfaces by an ultrasonic cleaner in tetra-
hydrofran. Films were prepared in vacuo (1 X lo4 torr)
with a controlled deposition rate of 1 A/s. The thickness
of the film was monitored and determined by a Sloan
thickness meter (DTM 200). The optical absorption
spectrum of the film deposited on quartz was measured
by a Hitachi 556 spectrophotometer. The amount of
porphyrin deposited was found to be the same for both
substrates, which was confirmed by measuring the solution
spectra of materials recovered from the film.
Excitation of the porphyrins was made by means of a
100-W tungsten lamp with a grating monochromator
(Nickon P-250). Exciting light intensity was calibrated
@ 1980 American Chemical Society