In the Laboratory

Determination of the Critical Micelle Concentration

of Cationic Surfactants
An Undergraduate Experiment
Xirong Huang,* Jinghe Yang, Wenjuan Zhang, Zhenyu Zhang, and Zesheng An
Department of Chemistry, Shandong University, Jinan 250100, P. R. China

Surfactants are amphiphilic compounds consisting of a is used as received. The concentrations of BPR, CPB, and
long-chain hydrocarbon “tail” and a polar (often ionic) CTAB solutions are 1.0 × 10᎑4 mol/L, 3.0 × 10᎑3 mol/L, and
“head”. In aqueous solutions, surfactant molecules can arrange 3.0 × 10᎑3 mol/L, respectively. A solution of approximately
themselves into organized molecular assemblies known as 0.8 mol/L of H2O2 is prepared by diluting the commercially
micelles if the concentration of the surfactant exceeds a certain available H2O2 (ca. 30% w/v) (A. R.) and is then standard-
value. The concentration at which micelles form is called the ized with KMnO4.
critical micelle concentration (cmc). The formation of micelles The following procedure is used. To a 10-mL graduated
greatly changes the properties of their medium, thereby tube with stopper, add an aliquot of an aqueous surfactant
affecting the chemical reactions taking place in the medium. solution (3.0 × 10 ᎑3mol/L) (warm the solution whenever
In recent years, there has been considerable interest in studies needed to avoid precipitation), 2.0 mL of 1.0 × 10᎑4 mol/L
of the effect of micelles on chemical reactions, or micellar BPR, 0.5 mL of 0.01 mol/L H2SO 4, and an appropriate
catalysis (1–3). It is therefore useful to introduce under- volume of distilled water to give a total volume of 7.0 mL.
graduate students to some basic concepts and physicochemical After mixing, add 3.0 mL of ca. 0.8 mol/L H2O2 and, at the
properties of surfactants, with a special emphasis on their same time, start the stopwatch. Quickly mix well and imme-
aggregates. Knowing about these helps students to answer diately transfer the solution to a cell. Then record the absor-
everyday-life questions (e.g., explain the washing power of a bance value at a time of 5 min and a wavelength of 574 nm
detergent) and arouses their interest in colloidal chemistry. for CTAB or 580 nm for CPB against distilled water.
Therefore, the determination of cmc’s of ionic surfactants is
of pedagogical interest. Results and Discussion
In the past, methods for the determination of the cmc
of ionic surfactants were based on the abrupt change of some Selection of Experimental Conditions
physicochemical properties such as conductivity or surface Acidity
tension in proximity to the cmc of surfactants (4). As an un- The rates of the indicator reaction differ greatly at dif-
dergraduate physicochemical laboratory experiment, these ferent pH values (adjusted with H 2SO 4). As the acidity
methods (5, 6 ) have disadvantages in terms of relevancy of decreases, the reaction rate decreases. One-half milliliter of 0.01
experimental content and technique to companion physico- mol/L H2SO4 has proven optimal. At such acidity (pH = 3.6),
chemical laboratory experiments (e.g., experiments on kinetics), H2O2 can barely oxidize BPR within 10 min. However, in
vitality in the program (introduction of new developments the presence of micelles of a cationic surfactant (CSF), the
in colloidal chemistry), information contained, complexity indicator reaction has a moderate reaction rate. Fortunately,
and availability of instruments, and toxicity of reagents. In at this acidity the effect of electrolyte (H2SO4) on the cmc is
this paper, a novel method based on micellar catalysis is negligible.
developed for undergraduates. Cetyltrimethylammonium Dye
bromide (CTAB) and cetylpyridinium bromide (CPB) catalyze
the redox reaction between H2O2 and bromopyrogallol red Bromopyrogallol red (BPR), a triphenylmethane dye, is
(BPR), a triphenylmethane dye, and this allows for the suitable for our purpose because the association complex of
measurement of cmc’s for CTAB and CPB. The indicator BPR with CSF is stable at the optimal pH. Moreover, the
reaction is monitored by a fixed-time kinetic spectrophotomet- molar absorptivity of the complex is great, assuring enough
ric technique. As an undergraduate physicochemical laboratory accuracy of the absorbance data (the error of a spectropho-
experiment, the present method has some attractive features. tometer is a minimum when absorbance values fall between
0.2 and 0.8) even when a relatively low dye concentration is
Experimental Procedure used to minimize the influence of the dye on the cmc.
Oxidant
The absorption spectra are recorded on a Shimadzu UV-
240 spectrophotometer using a matched pair of 10-mm The reasons why we choose H2O2 as the oxidizing agent
quartz cells. The cell compartment of the spectrophotometer is are that (i) H2O2 is uncharged and its reaction product is
thermostated by circulating water (25 °C) from its accessories. water; therefore, the effect of H2O2 on the cmc is negligible;
Unless otherwise stated, all solutions are prepared by and (ii) the change in absorbance after the formation of
weighing. Triply distilled water is used as the solvent. CPB micelles is significant (a plot of absorbance versus time shows
and CTAB are purified by recrystallization. BPR (E. Merck) that the indicator reaction is a pseudo-first-order reaction). In
the presence of micelles of a CSF, the reaction rate increases
with the increase of H2O2. To prevent any negative effect of
*Corresponding author. H2O2 on the determination of cmc, it is advisable to add

JChemEd.chem.wisc.edu • Vol. 76 No. 1 January 1999 • Journal of Chemical Education 93

 In the Laboratory

H2O2 in small amounts on the premise that the change of

the reaction rate in the proximity of the cmc is large enough

Reaction Rate / 75 min–1

to indicate the onset of micelle formation. The use of dilute
H2O2 solution minimizes the sampling error caused by the
poor stability of the concentrated H2O2 solution.
Data manipulation
1. Select a suitable wavelength (574 nm for CTAB or 580
nm for CPB) in the vicinity of the absorption maxi-
mum of the dye–CSF complex .
2. Record the absorbance value of the indicator reaction
(A2 ) and of its corresponding blank (A1) (without Concentration of CTAB / 10–4 mol/L
H2O2) at a given time (5 min).
3. Calculate the reaction rates (expressed as |A2 – A1|/5 Figure 1. Plot of reaction rate at 574 nm vs CTAB concentration.
min) at different concentrations of CSF.
4. Graph the reaction rate versus the final concentration physical chemistry. The information generated can be used
of CSF.
to elucidate the aggregation effect on the physicochemical
5. Connect the data points near to the cmc by straight
properties of surfactants and its possible application in sci-
lines and determine the cmc graphically. The intercept
of the two linear portions of the plot is considered the ence and technology as well.
onset of micelle formation (see Fig. 1 ). Third, the phenomenon surveyed by the experiment is
interesting, intuitive, measurable, and easy to interpret (5).
The obtained cmc values are (4.8 ± 0.3) × 10᎑4 mol/L and
The cmc values can be estimated without the need for data
(4.5 ± 0.3) × 10᎑4 mol/L for CTAB and CPB, respectively.
manipulation.
Applicability Fourth, the method is simple, rapid, and inexpensive.
Theoretically, the proposed method is applicable to both Neither an expensive fluorimeter (5) nor flammable pentane
cationic and anionic surfactants (in the latter case a cationic dye (6 ) is needed. All reagents are commercially available and
is needed). This method can be used whenever the micelles inexpensive. In addition, inaccurate setting of the wavelength
formed by the surfactant of interest have an obvious positive has little influence on the measurement of the reaction rate.
catalytic effect on a certain indicator reaction. A negative cata- Temperature fluctuations under nonthermostated conditions
lytic effect could not be utilized for our purpose because of (25 ± 5 °C) gives rise to an uncertainty of only ±7% (RSD).
the inevitable influence of electrolyte on the cmc. Therefore the method is also applicable for some labs where
no thermostating accessories are available.
Mechanism Last but not least, the effect of dye solubility in water
Micellar catalysis is different from chemical catalysis (1). on the accuracy of cmc determination is minimized. The cmc
The former is a physical phenomenon, while the latter is a values obtained by micellar catalysis are much closer to the
chemical process. Although micelles themselves are not involved literature values (4 ) of 9.2 × 10᎑4 mol/L (CTAB) and 9.0 ×
in the indicator reaction, the microenvironment provided by 10᎑4 mol/L (CPB) than those (0.9 × 10᎑4 mol/L for CTAB,
them, especially at the interface, can concentrate reactants 0.6 × 10᎑4 mol/L for CPB) determined by us with BPR based
involved in the indicator reaction via hydrophobic and elec- on micellar solubilization (7 ).
trostatic interactions. The intermediates, products, or both
can be stabilized, thereby enhancing the reaction rate. Acknowledgment
Advantages of the New Method We gratefully acknowledge financial support from the Key
First, it is a novel method based on micellar catalysis Laboratory for Colloid and Interface Chemistry of the State
rather than micellar solubilization as reported in this Journal Education Commission of China at Shandong University.
(5, 6 ). Micellar catalysis is a relatively new concept and is
of interest to students. Because micelles are similar in some Literature Cited
respects to cell membranes and micellar catalysis to enzyme 1. Perez-Bendito, D.; Rubio, S. Trends Anal. Chem. 1993, 12, 9.
catalysis (4), the present method may well be of interest to 2. Corsaro, G. J. Chem. Educ. 1973, 50, 575.
some instructors who are involved in developing a labora- 3. Huang, X.; Jie, N.; Han, S.; Zhang, W.; Huang, J. Mikrochim.
tory for membrane biochemistry or some similar course. Acta 1997, 126, 329.
Second, its content is informative and related to other 4. Zhao, G. Physical Chemistry of Surfactants; Beijing University Press:
Beijing, 1991.
companion physicochemical laboratory experiments. The 5. Rujimethabhas, M.; Wilairat, P. J. Chem. Educ. 1978, 55, 342.
technique used is an already existing one in kinetic experi- 6. Furton, K. G.; Norelus, A. J. Chem. Educ. 1993, 70, 254.
ments; therefore, introduction of the new concept does not 7. Huang, X.; Han, S.; Zhang, W.; Yin, Y.; Jie, N. Indian J. Chem.,
result in an increase in the total class hours of experimental in press.

94 Journal of Chemical Education • Vol. 76 No. 1 January 1999 • JChemEd.chem.wisc.edu