Colloids and Surfaces, 40 (1989) 219-226 219

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

Interaction of Tri-iodide Ion with Anionic

Surfactant Micelles in Aqueous Solution

JUNG-HUNG CHANG, MAKOTO OHNO, KUNIO ESUMI and KENJIRO MEGURO

Department of Applied Chemistry and Institute of Colloid and Interface Science, Science
University of Tokyo, Kagurazaka, l-3 Shinjuku-ku, Tokyo (Japan)
(Received 2 August 1988; accepted 15 February 1989)

ABSTRACT

The color of an aqueous tri-iodide ion (I,-) solution fades in the presence of anionic surfac-
tants, such as sodium dodecyl sulfate (SDS), sodium di-2-ethylhexyl sulfosuccinate (Aerosol OT)
and sodium 4-sulfobutyl laurate (llC-4), when the added concentration of anionic surfactant is
above the c.m.c. These results can be explained by the acceleration of hydrolysis of Is- in the
presence of negatively charged micelles. The hydrogen ions are sequestered by anionic micelles
from the aqueous solution, resulting in a change in the bulk solution property due to hydroxyl ions
remaining after the fixation of protons at the micelles, and leading to an increase in the rate of
hydrolysis of I,-. Further, the fading of I,- in aqueous solution depends on the type of surfactant
and the concentration of sodium chloride. Above the surfactant c.m.c. the fading of the color of
the Is- solution becomes slower with increasing concentration of sodium chloride, eventually
reaching zero, except in the case of SDS. This salt effect can be explained by the exchange between
hydrogen and sodium ion at the surface of the anionic micelle.
The magnitude of hydrolysis of I,- in the various anionic surfactants in the presence of sodium
chloride occurs in the following order: AOT> llC-4> SDS.

INTRODUCTION

There have been several early studies of the hydrolysis of iodine [l-5]. Bray
[ 21 found that the increase in conductance of an aqueous iodine solution with
time depended on the hydrolysis reaction of iodine in the aqueous solution.
This hydrolysis of iodine is accelerated by an excess of hydroxyl ion [ 31. More
recently, Uehara [6] reported that the inhibition of the coloring reaction in
the amylose-iodide system by the presence of alkali is caused by a decrease in
the amount of tri-iodide ion (Is- ) which forms the amylose-iodine complex.
On the other hand, iodine is an electron acceptor which forms complexes
with nonionic surfactants [7-121. This property of iodine has been used to
determine the c.m.c. of nonionic surfactants by Ross and Oliver [ 71 and Becher
[S]. However, Ross and Oliver [7] and Chao et al. [ 131 have reported that
only a very weak interaction takes place between iodine and negatively charged

0166-6622/89/$03.50 0 1989 Elsevier Science Publishers B.V.

220

micelles, such as sodium dodecyl sulfate (SDS). Where iodine shows a very
weak maximum absorption band at 460 nm [ 14,151, this sensitivity is too low
to obtain any information about micelle formation by anionic surfactants. While
hydrogen ion is expected to be adsorbed at negatively charged micelles in weakly
acid solution [ 16,171, some interaction between Is- (or IZ) and the anionic
surfactant could occur in this case.
When iodine and iodide ion exist in the same solution and the concentration
of iodine is smaller than that of iodide, the tri-iodide ion is mainly formed
[ 18,191, and this has a high absorbance coefficient at 350 nm [ 141. In this
work the interaction between iodine and anionic surfactants, such as SDS,
sodium di-2-ethylhexyl sulfosuccinate (AOT) and sodium 4-sulfobutyl laurate
(llC-4), was studied by monitoring the change in absorbance of 13-.

EXPERIMENTAL

Materials

Sodium dodecyl sulfate (SDS) was synthesized according to the modified

method of Dreger et al. [ 201, using acetic acid instead of chloroform as the
solvent for dodecanol. The crude product was purified by repeated recrystal-
lization from ethanol or an isopropanol-water mixed solution and extraction
with ethyl ether. The purity of this sample was confirmed by surface tension
measurements.
Sodium di-2-ethylhexyl sulfosuccinate (AOT) was supplied by the Nikko
Chemical Co. Ltd and its purity was above 98%. The sample was confirmed to
be highly pure by the absence of a minimum in a plot of surface tension versus
log (concentration). The surface tension curve obtained in this experiment
agreed well with that obtained with an elaborately purified sample by Williams
et al. [21]. Its critical micelle concentration (c.m.c.) was 2.5 mM in water at
25°C.
Sodium 4-sulfobutyl laurate (llC-4) was prepared from esterification of
lauric acid with butane sulfone by Hikota in our laboratory [ 221. The product
was recrystallized three times from methanol and then extracted for 100 h with
petroleum ether to yield a white, flaky powder. The structure of llC-4 is as
follows: C&H&O0 (CH,),SO,Na.
Iodine and potassium iodide were guaranteed grades supplied by the Hiko-
taro Shudzui Co. Ltd. Iodine was purified with potassium iodide by the subli-
mation method.
Water was purified by passage through a Mill-Q system (Nihon Milli Pore
Co.) until its specific conductivity fell below lop7 a-’ cm-‘.
 221

Measurements

The absorption spectra of iodine in each sample were measured at 25 “C

using a spectrophotometer (Hitachi type 220A). All measurements were car-
ried out within an hour following the preparation of the samples.

RESULTS AND DISCUSSION

Figure 1 shows the absorption spectra of IB- (12=0.1 mM, KI= 0.36 mM)
at 250-450 nm in SDS aqueous solution. The absorption maximum band of
I,- at 350 nm does not shift in the presence of SDS, but the absorbance of Is-
decreases with the concentration of SDS above its c.m.c. If iodine had been
used in this experiment in the absence of potassium iodide it would have shown
a very small maximum absorption band at 460 nm [ 14,151. The change in
absorbance of iodine at 460 nm is not sensitive enough for one to study the
interaction of an anionic surfactant with iodine upon the addition of the an-
ionic surfactant [ 131. Consequently, in order to study this interaction, it is
essential to use potassium iodide in these mixtures.
Plots of the absorbances of IB- (I, = 0.1 n-&f, KI = 0.36 mM) at 350 nm against
log C for anionic surfactants in aqueous solution are shown in Fig. 2. In the
case of AOT, a break point appears at 3.2 mM AOT, where the absorbance of
I,- decreases with the concentration of AOT above 3.2 mM. This concentra-
tion of AOT (3.2 mM) almost corresponds to the c.m.c. (2.5 mM) obtained by
surface tension measurements [ 211. Similar behavior is observed in the case
of llC-4; here the breakpoint appears at 3.6 mM. This value also agrees with
that obtained by conductivity measurements [ 221. The c.m.c. values of anionic

IO
Wavelength (nm)

Fig. 1. The absorption spectra of Is- at 250-450 nm in SDS aqueous solution.

 -3 SDS
06 Q llC-4

+ AOT

0.2

10-L I o-3 10-2

Concfnlrationof surfactant CM)

Fig. 2. The absorbances of I- at 350 nm plotted against log C of the anionic surfactants.

TABLE 1

Values of the c.m.c. of the anionic surfactants used in this study

Chemical structure Abbreviation c.m.c. (mM)

Iodine Surface Conductivity

solubilization tension

C,,H,,OSO,Na SDS 7.6 7.7 [23] 8.1 [24]

C,H,,OOCCH,
I AOT 3.2 2.5 [21] 5.5 [25]
C,H,,OOCCHSO,Na
W-I&OO(CH,)$O~Na llC-4 3.6 2.5 [22] 3.3 [22J

surfactants determined by iodine solubilization, surface tension and conduc-

tivity measurements are listed in Table 1.
On the other hand, the maximum absorption band of I,- at 350 nm is shifted
towards 370 nm, and the absorbance increases with the concentration of a
nonionic surfactant, hexaoxyethylene glycol dodecyl ether (6ED ), above its
c.m.c. This result is attributed to a complex formed between IB- and 6ED [ 141.
However, the fact that the absorbance of IB- decreases in the presence of an-
ionic surfactants indicates that these negatively charged micelles have some
effect in mixed surfactant solutions. When an anionic surfactant micelle is
formed in aqueous solution, the micelle surface has a strong negative charge as
compared with a surfactant monomer. Since the negatively charged AOT mi-
celle will fix hydrogen ions near its surface, the unfixed hydroxyl ion in the
bulk aqueous solution provides a basic environment. These hydroxyl ions ac-
celerate the hydrolysis of 13-. The hydrolysis reaction of IB- is given by the
following steps:

Is- +H,O=I- +I,+H,O=I- +HIO+I- +H+ (1)

 223

313-+3Hz0~31-+312+3H20~31-+I0,-+51-+6H+ (21
The fraction of overall iodine present as I2 decreases sharply in the pH range
6-10, since I2 is replaced by I- and IO,- [ 261. The hydrolysis of Is- proceeds
very slowly at pH 5-6, but the reaction is considerably accelerated by the pres-
ence of anionic surfactant micelles.
In Fig. 3 the absorbances of IB- (I, =O.l mM, KI=0.36 mM) at 350 nm
against log C of AOT are shown as a function of the concentration of added
sodium chloride. The absorbance of Is- decreases very sharply above the c.m.c.
of AOT in the absence of sodium chloride, but the addition of 5-7.5 mM of
sodium chloride makes the magnitude of the decrement smaller. Finally, the
addition of 10 mM sodium chloride makes the decrement zero, and the I,-
solution almost maintains the same absorbance with AOT even above its c.m.c.
With an increase in the concentration of sodium chloride, the fixed concentra-
tion of counterion at the micelle surface increases, so that the basicity of the
surrounding bulk aqueous solution disappears; the hydrolysis of Is- hardly
occurs in the presence of sodium chloride in concentrations exceeding 10 mM.
This salt effect can be explained by H+/Na+ ion exchange [ 271 at the surface
of the anionic micelle. In addition, the concentration at the breakpoint corre-
sponding to the c.m.c. decreases with increasing concentration of sodium chlo-
ride [ 28,291. These concentrations almost coincide with the c.m.c. values ob-
tained by surface tension measurements [ 301.
Figure 4 shows the absorbance of IB- (I,=O.l mM, KI =0.36 mM) at 350
nm plotted against log C of SDS as a function of the concentration of sodium
chloride. The total absorbance of I,- decreases sharply at the c.m.c. of SDS.
However, this breakpoint becomes less sharp after the addition of sodium chlo-
ride. In this mixture the inhibition of the hydrolysis of IB- by the addition of
sodium chloride should occur. In the case of SDS, the hydrolysis of I,- can still

0.2-

10-4 lO-3 lo-*

Concentration of AOT (M)

Fig. 3. The absorbances of IB- at 350 nm plotted against log C of AOT as a function of the con-
centration of sodium chloride.
224

Noel 0 0 mM

* 75

0.6 -D 20

+ 100

0.2

I ci4 I o-3 Ki*

Concentration of SDS (M)

Fig. 4. The absorbances of I,- at 350 nm plotted against log C of SDS as a function of concentra-
tion of sodium chloride.

-b iodine sofubilizotlon

I o-2 10-l
Concentration of Nacl (M)

Fig. 5. The c.m.c. of SDS in the presence of sodium chloride.

take place at a high concentration of sodium chloride in comparison with the

case of AOT. On the other hand, Knox [31] found that SDS micelles clearly
provide protons to form a complex with gelatin in the presence of sodium chlo-
ride, while for AOT micelle, complex formation with gelatin is not observed.
AOT, having an ester group, is considerably different from SDS in structure.
When a loose micelle is formed in some anionic surfactant solutions, the degree
of counter-ion dissociation of the micelle is large. The degree of counter-ion
dissociation in AOT is higher than that for SDS: 0.4 for AOT [ 321 and 0.25 for
SDS [ 33,341. M oreover, since the AOT molecule contains a bulky alkyl group,
it will provide the loosest micelle of the three kinds of anionic surfactant. Thus
the above result indicates that the charge density on the surface of the SDS
micelle is high in comparison with the case of AOT.
In the case of I,- with SDS (Fig. 4), the c.m.c. of SDS also decreased with
an increase in the concentration of sodium chloride [ 311. Results for the c.m.c.
of SDS in the presence of sodium chloride obtained by iodine solubilization
 225

Nacl Q 0 mhl

0.6 - * 75
43 20
0 100
J
0’
s! OA-
s
.a
Q

0.Z

10-4 10-3 Io-2

Concentration of llC-~5 (MI

Fig. 6. The absorbances of Ia- at 350 nm plotted against log C of llC-4 as a function of the
concentration of sodium chloride.

and surface tension measurements are shown in Fig. 5. The c.m.c. values of
SDS obtained from both methods are very similar.
In the case of llC-4, plots of the absorbances of IB- (1, = 0.1 mM, KI = 0.36
mM) at 350 nm against log C of llC-4 are shown in Fig. 6 as a function of the
concentration of sodium chloride. Upon the addition of 100 mM sodium chlo-
ride, the IB- solution also maintained the same absorbance with llC-4, even
above its c.m.c. This concentration is larger than that of AOT.
From the concentrations of sodium chloride obtained in the cases of IB- with
SDS, AOT and llC-4, respectively, the hydrolysis reaction of IB- for the var-
ious types of anionic surfactant is affected by sodium chloride in the following
order: AOT > llC-4 > SDS.

REFERENCES

V. Sammet, Z. Phys. Chem., 53 (1905) 689.

W.C. Bray, J. Am. Chem. Sot., 32 (1910) 932.
R.L. Taylor, J. Chem. Sot., 77 (1900) 726.
H.D. Murray, J. Chem. Sot., 127 (1925) 882.
Ch. Wintter, Z. Phys. Chem., Abt. B, 3 (1929) 313.
S. Uehara, Nippon Shokuhin Kogyo Gakkaishi, 33 (1986) 487.
S. Ross and J.P. Oliver, J. Phys. Chem., 63 (1959) 1671.
8 P. Becher, J. Phys. Chem., 63 (1959) 1675.
9 P.H. Elworthy, J. Pharm. Pharmacol., 12 (1960) 293.
10 T. Kenjo and T. Matsumoto, J. Jpn. Oil Chem. Sot., 10 (1961) 418.
11 T. Kenjo and T. Matsumoto, J. Jpn. Oil Chem. Sot., 10 (1961) 683.
12 J.E. Carless, R.A. Challis and B.A. Mulley, J. Colloid Sci., 19 (1964) 201.
13 C.S. Chao, S. Muto and K. Meguro, Nippon Kagaku Kaishi, (1972) 1570.
14 J.H. Chang, M. Ohno, K. Esumi and K. Meguro, J. Am. Oil Chem. Sot., 65 (1988) 1664.
15 A.D. Awtreyand and R.E. Connick, J. Am. Chem. Sot., 73 (1951) 1842.
16 J.L. Kurtz, J. Phys. Chem., 66 (1962) 2239.
226

17 V.A. Motsavage and H.B. Kostenbander, J. Colloid Sci., 18 (1963) 603.

18 J.N. Pearce and W.G. Eversole, J. Phys. Chem., 28 (1924) 245.
19 U. Shibada, Inorganic Chemistry (III): Halogen, Maruzen, Tokyo, 1958 pp. 297-298.
20 E.E. Dreger, G.I. Keim, G.A. Miles, L. Shedlovsky and J. Ross, Ind. Eng. Chem., 36 (1944)
610.
21 E.G. Williams, N.T. Woodberry and J.K. Dicon, J. Colloid Sci., 12 (1957) 452.
22 T. Hikota, Bull. Chem. Sot. Jpn., 43 (1970) 2236.
23 H. Akasu, M. Ueno and K. Meguro, J. Am. Oil Chem. Sot., 51 (1974) 519.
24 K.J. Mysels and R.J. Otter, J. Colloid Sci., 16 (1961) 462.
25 J.H. Chang, unpublished work.
26 D.A. Palmer and M.H. Lietzke, Radiochim. Acta, 31 (1982) 37.
27 F.H. Quina, M.J. Politi, I.M. Cuccovia, S.M. Martins-Franchetti and Chaimovich, in K.L.
Mittal and E.J. Fendler (Eds), Solution Behaviour of Surfactants: Theoretical and Applied
Aspects Vol. 2, Plenum Press, New York, 1982, p. 1125.
28 K. Shinoda, Kagaku To Kogyo, 14 (1961) 137.
29 A.M. Kragh, Trans. Faraday Sot., 60 (1964) 225.
30 W.J. Knox Jr and T.O. Parshall, J. Colloid Interface Sci., 40 (1972) 290.
31 W.J. Knox Jr and T.O. Parshall, J. Colloid Interface Sci., 33 (1970) 16.
32 M. Ueno and S. Natsume, Research Report, Department of Pharmacology City University
of Nagoya, 24 (1976) 39.
33 P. Mukerjee, K.J. Mysels and P. Kapauan, J. Phys. Chem., 71 (1967) 4166.
34 T. Ingram and M.N. Jones, Trans. Faraday Sot., 65 (1969) 297.