Substrate Partitioning and Chemical Equilibrium
in a Micellar Solution
Elsa B. Abuin and Eduardo A. Lissi
Departamento de Quimica, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Correo 2, Santiago, Chile
Micellar solutions can be considered microheteroge-
neous svstems. The ex~erimentwe describe in this article
is desighed to study one very important aspect of these so-
lutions that is due to their microhetero~eneouscharacter:
As a solute is dissolved, it is inhomoge&ously distributed
throughout the entire volume of the resulting solution.
The experiment is used to determine the distribution of
iodine between a micellar pseudophase, formed by sodium
dodecylsulfate micelles, and the intermicellar aqueous
phase. This is achieved by measuring the effect of adding
surfactant on the following reversible reaction.
Introduction
Micellar solutions are formed by dissolving certain types
of surfactants in water. The surfactants that form micelles
are amphiphilic molecules whose structures simulta-
neously bear one (rarely more) hydrophobic chain (typi-
cally an alkyl chain with at least 6-8 methylene groups)
and a polar head group (typically a n ion or very hydro-
philic group). The unique structure of this type of mole-
cule, with its hydrophobic and hydrophilic character, is re-
quired to form micelles.
Dissolved surfactants in water display different behav-
ior depending on the range of concentration considered. At
low concentrations they dissolve as isolated molecules. At
high concentration, dissolution occurs with self-associa-
tion of the surfactant molecules into aggregates of colloidal
dimensions (radii of about 1.5-2 nm), called "micelles".
The self-association of the surfactant molecules is strongly
cooperative. The onset of micelle formation, which marks
the change from dissolution as monomers to dissolution as
aggregates, occurs in a very narrow concentration range--
virtually a t a single concentration.
There are two fundamental models used to interpret the
associr~tionof surfactant into micelles. One is theequilib-
rium model in which micelle formation is treated as being
analogous to a chemical equilibrium. The other is the
phase separation model in which micelle formation is con-
sidered to be analogous to a phase separation.
According to the phase separation model (psm), the con-
centration that corresponds to the onset of micelle forma-
tion is considered to be the saturation concentration of the
surfactant in the monomeric form. It is called the critical
micelle concentration ~ C M C IThc
. micelles are condidered
to constitute a separated pseudophase. The psm will be op-
erationally convenient for our study.
Regardless of the model used to explain the formation of
the micellar aggregates, a micellar solution can be de-
scribed as a system of hydrophobic domains of colloidal di-
mensions. These domains are represented by the micelles
(the micellar pseudophase in the psm) immersed in a dis-
persion medium or intermicellar phase, which is the aque-
ous phase containing surfactant at a concentration equal
Correspondence should be addressed to E. 6. Abuin.
340 Journal of Chemical Education
to the CMC in the psm. Certainly, such a system will be-
have as microheterogeneous.
When a solute is added to a solution of this type, a so-
lute-containing micellar solution is formed in which the so-
lute is inhomogeneously distributed. There will be a t least
three zones (1-5)available to the solute as solubilization
loci:
The "bulk" of the micellar pseudophase, which is the micelle
core and represents something like a hydrocarbon solvent
The aqueous phase
The interface between the micellar pseudophase and the
aqueous phase
I t is sometimes convenient to make no distinction be-
tween the bulk of the micelles and the interface. In other
words, consider that the assembly of all micelles is the only
distinct phase existing in the solution besides the aqueous
phase. Then we can treat the solute distribution as a par-
titioning between just two phases: t h e micellar
pseudophase and the aqueous phase. This will be the ap-
proach used in this experiment in which we interpret the
partitioning of iodine in sodium dodecyl sulfate (SDS) mi-
cellar solutions.
Reaction in Water Without Surfactant
Adding iodide to an aqueous iodine solution will increase
the absorbance a t 353 nm, which corresponds to the pres-
ence of triiodide ion (6).The equilibrium constant for the
reaction of eq 1 can be obtained by measuring absorbance
a t 353 n m as a function of the amount of iodide added to an
aqueous iodine solution. Assuming dilute solution behav-
ior, we get
where x is the concentration of triiodide formed; a is the
total concentrations of iodine, and b is the total concentra-
tion of iodide.
Substituting y = x/a and z = bla, eq 2 can be rearranged.
The value of y is obtained experimentally. It is the ratio
between the absorbances a t 353 nm measured for two dif-
ferent solutions: a solution with a given concentration of
iodine and iodide, and a solution in which the iodine is con-
verted completely to triiodide ion by addition of excess io-
dide. Plotting the left hand side of eq 3 against (z -y) yields
a straight line whose slope is the value of K.
Reaction With Surfactant
In the uresence of surfactant. iodine will be ~artitioned
between ihe micellar pseudophase and the aqueous phase,
whlle iod~deand triiodide will be solubilized exclusivelv in
the aqueous phase. Since these hydrophilic ions a r e
charged, their interaction with the micellar pseudophase
is prevented by wulombic repulsion. Thus, in the presence
of surfactant, the reaction scheme can he represented as
below.
Equations 4 and 5 show that adding SDS to a given Ifl-
solution in water will decrease the production of triiodide
as compared to the amount formed in the same Ifl- solu-
tion without surfactant. Extraction of part of the iodine to
the micellar pseudophase will diminish the amount of io-
dine available in the aqueous phase to react with the io-
dide. The concentration of (I&, which affects the reaction
in the aqueous phase, will be subjected to the partition
equilibrium condition given in eq 4.
To obtain the partition constant, the amount of iodine in
the micellar ~ s e u d o ~ h amust
s e be emressed in terms of its
intramicellar concentration. Asuitableconcentration scale
can be defined cat low incorporation values, as below.
=meiated is the analytical concentration of io-
where [Izlrnieelle
dine associated with the micelles (mol iodine& of solution);
and [SDSIMis the concentration of micellized surfactant. I t
is given by
[SDSIM= [SDSllbtsll - CMC (7)
The partition constant Kp for the phase equilibrium of eq 4
is then given by
Next we combine eqs 2,4,5, and 8, taking into account the
mass balance condition of eq 9. We neglect the volume oc-
cupied by the micellar pseudophase.
Equation 10 can be derived.
where y' has the same meaning as y in eq 2, but here it
applies to the results obtained in the presence of surfac-
tant.
A straight line is obtained from plotting the left hand
side of eq 10 against l/(z -y'), using results obtained from
experiments in which the concentrations of iodine and
SDS were kept constant, while the concentration of iodide
was varied. K, is obtained fmm the slope of the line.
slope - 1
K
P
--
- [SDSI.
Experimental
Sodium dodecylsulfate (BDH, specially pure) was used
as received. Iodine (Merck) was purified by sublimation.
Potassium iodide (Merck)was used without treatment.
Two solutions of iodine in water were prepared, titrated
following standard methods, and used thmughout the ex-
periments. The concentrations of these solutions were
0.183 and 0.366 mM. A stock solution of potassium iodide
in water (0.1 M) was prepared, titrated following standard
methods, and used throughout the experiments.
Absorption spectra and absorhances were recorded ona
Shimadzu W-160 spectmphotometer that was equipped
with a thermoregulated cell compartment. The experi-
ments were done a t 21 T. (This was also the temperature
of the mom.)
For each iodine concentration considered the experi-
ments were performed as follows.
Without Surfactant
Iodine solution (3 mL) was delivered into the cuvette of
the spectrophotometer (rectangular; pathlength: 1 em),
and the spectrum was recorded at 300-650 nm. This spec-
trum had a bmad hand a t 460 nm, corresponding to the
absorption of iodine in water, and a very weak absorption
a t 353 nm. The absorbance at 353 nm for this starting so-
lution is recorded and used as a background signal to be
subtracted from the readings taken in the presence of io-
dide. Aliquots of2 pLof the potassium iodide stock solution
were added to the starting solution in the cuvette in
succesive steps to a total addition of 20 pL. ARer each ad-
dition, the mixture is homogeneized by manual shaking,
and the absorbance a t 353 nm is recorded.
With Surfactant
Four solutions were prepared in which the solvents used
were the same iodine solutions used in the experiments
done without surfactant.
0.05 M and 0.1 M SDS in which the 0.183m M iodine solu-
tion was used as the solvent
0.05 M and 0.1 M SDS in which the 0.366mM iodine solu-
tion was used as the solvent.
Each of these solutions were used following the same pm-
cedure described for the experiments without surfactant.
Results And Discussion
Iodine concentrations considered were 0.183 mM and
0.366 mM. The production of IB-was followed by measur-
ing the absorbance of the solutions a t 353 nm a h r addi-
tion of increasing amounts of iodide. The range of iodide
concentrations considered was 0.066-0.66 mM.
Figure 1 shows the results obtained for the reaction in
water without SDS, plotted according to eq 3. The linearity
of the plot indicates that, under the experimental condi-
tions used, the assumption of diluted behavior is reason-
able. The slope of the line shown in Figure 1 gives
K = 783 f 19 M-'. Experiments carried out with surfactant
used two different concentrations: 0.05 and 0.1 M.
For each SDS concentration, the iodine concentrations
considered were the same as those used for the reaction in
water without surfactant. Figure 2 shows the results ob-
tained, plotted according to eq 10. In the figure, the results
obtained using both iodine concentrations lie on the same
line for each surfactant concentration, and the slope of the
line is larger for the highest surfactant concentration.
These are the expected behaviors because iodine partition-
ing between the micellar pseudophase and the aqueous
phase must be independent of the iodine concentration and
because the slope of the line is a direct function of SDS
concentration (see eq 10).
From the slopes of lines A and B of Figure 2, K, is calcu-
lated as
slope - 1
Kp = --
[SDSI,
using [SDSIMfrom eq 7 with CMC = 0.008 M (7).Both sets
of experiments give very similar values for K,.The values
for Kp obtained from the experiments are
Volume 69 Number 4 April 1992 341
 Kp = 17 i 0.5 M-' when the concentration
of SDS is 0.1 M
Kp = 17.2 f 0.8 M-l when the concentration
of SDS is 0.05 M
This is consistent with the definition of Kp
(see eq 8) in which it is considered to be
independent of the surfadant concentra-
tion. The value ofKp obtained implies that
50% of the iodine is associated with the
micelles (with no added iodide) when the
SDS concentration is 0.067 M. Also. the
value ofK, implies that, at SDS = 0.067 M,
the concentration of iodine in the micellar
pseudophase (81, defined in moles of solute
per liter of micellar pseudophase, is nearly
25 times the analytical iodine concentra-
tion.
This higher concentration of the solute
in the micellar pseudophase is one of the
most relevant characteristics of the solu-
tions of surfadants. I t explains their main
e s as solvents and as reaction
~ r o ~ e r t iboth
Figure 1. Results obtained for the reaction in water without surfactant, plotted according to to increase the rate of bimolecular
eq 3. Temperature: 21'C. Iodine mncentrations: 0.183 mM (0)and 0.366 mM (+). processes ( 9 , I O ) .

Acknowledgment
Thanks a r e given to FONDECYT
(Grant#775/90) for financial support.

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342 Journal of Chemical Education