Colloids and Surfaces

A: Physicochemical and Engineering Aspects 143 (1998) 89–94

Determination of the first and second CMCs of surfactants by

adsorptive voltammetry
Chengsong Ma a,b, Ganzuo Li a, Yongming Xu a, Hanqing Wang b, Xingfu Ye c
a College of Chemistry, Shandong University, Jinan, 250100, China
b Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, China
c Department of Chemistry, Jinan University, Jinan, China
Received 26 November 1997; accepted 24 April 1998

Abstract

The first and second critical micellar concentrations (CMCs) of sodium dodecylsulfate and cetyltrimethylammonium
bromide were determined by adsorptive voltammetry with an electrochemical probe. The distribution of probe inside
and outside the micelle at the second CMC was calculated. The electrode reaction mechanism of the probe on the
hanging mercury drop electrode is also discussed. © 1998 Elsevier Science B.V. All rights reserved.

Keywords: Critical micellar concentration; Adsorptive voltammetry; Surfactants

1. Introduction of cetyltrimethylammomum bromide (CTAB) and

When the concentration of a surfactant is
increased, its structure may change from single
molecules to spherical, rod- and lamellar-shaped
micelles. Spherical micelles are formed at the first
critical micellar concentration (CMC ). The second
CMC indicates the structural transition from
spherical micelles to rod-like ones. Many methods
have been used to determine the first CMC such
as surface tension, conductivity, solubilization, and
light scattering [1]. These methods are simple and
easily utilized. However, few techniques have been
applied to determine the second CMC. Miura et al.
determined the second CMC of SDS by four
methods [2–5]. Li Fang et al. [6 ] determined the
second CMC of several surfactants by the fluores-
cence probe technique.
Electro-analytical methods are relatively simple
and cheap. Mandal [7] used the cyclic voltammet-
ric technique for the determination of the CMC
cetylpyridinium chloride (CPC ). Krichmar [8] put
forward a polarographic method for the determi-
nation of the critical concentration of micelle for-
mation in dye solutions. Cyclic voltammetric
techniques without a probe have also been used
to determine the first and second CMCs [9].
Adsorptive voltammetry is one kind of voltam-
metric analytical method which has been developed
over the last 30 years [10,11]. It is extremely
effective in the analysis of organic compounds,
because many organic compounds can be adsorbed
onto the electrode. If the appropriate preconcen-
tration condition is selected, the compound accu-
mulated on the electrode, and the sensitivity of the
adsorptive voltammetry is better than other vol-
tammetry techniques. In this paper, we used the
more oil-soluble, but less water-soluble ‘‘neutral
red’’ as the electro-active probe. When a micelle is
formed, neutral red is solubilized into the micelle.
After a rod-like micelle is formed, the concen-

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90 C. Ma et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 143 (1998) 89–94
tration of neutral red outside the micelle decreases
sharply. The trace neutral red can be accumulated
on the hanging mercury drop electrode, allowing
its determination after the rod-micelle is formed.
Thus adsorptive voltammetric technique with neut-
ral red as a probe is used to determine the first
and second CMCs. The electrode reaction mecha-
nism of neutral red on a hanging mercury drop
electrode in the micelle system is also discussed.
2. Experiment
2.1. Materials and reagents
CTAB was purchased from Jining Chemical
Company and purified by three crystallizations
from ethanol/acetone. Sodium dodecylsulfate
(SDS) was also obtained from Jining Chemical
Company and was recrystallized twice in ethanol.
3-Amino-6-dimethylamino-2-methylphenazine
hydrochloride (neutral red) was obtained from
Beijing Chemical Company. Ethanol and acetone
were analytical grade reagents, water used was
doubly distilled.
A Jp -1 voltammetric analyzer (Shandong No.7
3
electric factory, China) was used in connection
with a self-made cell, using a three-electrode system
which consists of a hanging mercury drop electrode
(HMDE) as the working electrode, a Pt plate
electrode as the counter electrode and a saturated
calomel reference electrode (SCE ). A model 173
potentiostat/galvanostat accompanied by a model
179 digital coulometer (PARC, USA) was used to
measure the charge, the working electrode being a
mercury cell electrode.
2.2. Sample preparation
2×10−4 mol l−1 neutral red stock solution was
prepared by dissolving 0.0058 g neutral red in an
alcohol/water mixed solution; 0.01 mol l−1 and
0.05 mol l−1 CTAB stock solution was stored
in a 30°C thermostated container while
5×10−2 mol l−1 and 0.5 mol l−1 SDS stock solu-
tions were kept in a 40°C thermostated container.
Each diluted surfactant solution which contained
1×10−6 mol l−1 neutral red was stored in the
thermostated container for 24 h before being ana-
lyzed by voltammetry.
2.3. Procedure
The diluted surfactant solution (containing neut-
ral red) was transferred into the cell and deoxyge-
nated with nitrogen (99.99%) for 15 min. The pre-
concentration potential was applied to a fresh
mercury drop. Following a pre-concentration
period the stirring was stopped, and after 10 s the
voltammogram was recorded by applying a linear
reductive scanning potential. Each measurement
was performed with a fresh drop.
3. Results and discussion
3.1. Adsorptive voltammogram of two surfactants
system
Fig. 1 shows the adsorptive voltammograms of
the CTAB–neutral red system and the SDS–neutral
red system. CTAB or SDS solution in the absence
of neutral red has no obvious reductive peak (see
curves a and d). This means that neither CTAB
nor SDS is reduced on an HMDE. CTAB–neutral
red gives one reductive peak at −0.72 V and two
small oxidation waves at −0.50 and −0.62 V
Fig. 1. Adsorptive voltammogram of two surfactants system
(scan speed=345 mV s−1; t =90 s; E =−0.1 V (vs. SCE)):
a a
curve a, 6.5×10−4 mol l−1 CTAB; curve b, a+1×
10−6 mol l−1 neutral red; curve c, 6×10−3 mol l−1
SDS+1×10−6 mol l−1 neutral red; curve d, 6×10−3 mol l−1
SDS.
 C. Ma et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 143 (1998) 89–94 91

(curve b). However SDS–neutral red gives two

reductive peaks—one at −0.75 V and the other
at −1.02 V and no obvious oxidation peak appears
(curve c). Experimental results showed that the
reductive peak potential (E ) of neutral red in the
p
surfactants solution shifted in the negative direc-
tion when the potential scan rate increased. There
are no corresponding oxidation peaks on the cyclic
voltammogram. These results suggest that the
reduction of neutral red in CTAB and SDS solu-
tions is irreversible. The oxidation and reduction
behavior of neutral red was different in these two
surfactant systems. We will discuss this in another
paper. In the current study, the peaks at −0.72
and −0.75 V are used as the reductive peak of
neutral red in the CTAB and SDS system
respectively.
The following experimental factors affect the
shape of voltammetric curve: pre-accumulation
potential, scan-end potential, pre-accumulation
time, scan rate of potential. The best analytical
result was achieved with the following conditions:
pre-accumulation potential of −0.10 V (vs. SCE ),
scan-end potential of −1.20 V, pre-accumulated
time of 90 s and scan speed of 345 mV s−1.

3.2. Determination of the first and second CMCs

In this section, the concentration of neutral red
was fixed while that of the surfactants was varied.
The adsorptive voltammogram of each neutral
red–surfactant system was recorded in order to
measure the peak current (i ) of neutral red. The
p
relationship between peak current and the concen-
tration of surfactants is shown in Fig. 2, it can be
seen that i is constant before a threshold surfac-
p p
tant concentration is reached and above this
threshold i decreases. The two turning points
p s
are 8.8×10−4 mol l−1 for CTAB and
8.3×10−3 mol l−1 for SDS respectively, these
values being similar to the first CMC value in
Refs. [12,13]. Curve a and curve b can be explained
as follows. Before the first CMC, surfactants exist
in their monomer form and all the neutral red can
be determined. After the spherical micelles are
formed, a certain portion of neutral red enters into
micelles. Its concentration reduces, while the i
p
decreases. With increasing micelle number, more
Fig. 2. Relationship between the peak current of neutral
red and the concentration of the surfactants: curves a, a∞,
CTAB; curves b, b∞, SDS. Concentration of neutral
red=1×10−6 mol l−1. Other experimental condition as in
Fig. 1.
neutral red enters into micelles, and the i continues
p
to decrease.
From curve a∞, we can see that i falls slightly
if c <7.0×10−3 mol l−1 but falls steeply when
s
c >7.0×10−3 mol l−1. It is the same for curve b∞
whose turning point is at 6.3×10−2 mol l−1. When
the shape of the micelle changes from a sphere to
a rod, the solubility of neutral red into the micelle
increases, the i decreases even deeply, thus the
p
curves of i –c have turning points. The two turn-
p s
ing points correlate with second CMC values
reported in the literature, at which the micellar
aggregates are known to change form. The second
CMC are 7.0×10−3 mol l−1 for CTAB and
6.3×10−2 mol l−1 for SDS respectively. These
92 C. Ma et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 143 (1998) 89–94

Fig. 3. Relationship between peak current of neutral red in

the surfactants system and equilibrium time: curve a, Fig. 4. Effect of pre-accumulation time on peak current: curve
1×10−3 mol l−1 CTAB+1×10−6 mol l−1 neutral red; curve a, 6.5×10−4 mol l−1 CTAB+1×10−6 mol l−1 neutral red;
b, 1×10−2 mol l−1 SDS+1×10−6 mol l−1 neutral red. Other curve b, 6×10−3 mol l−1 SDS+1×10−6 mol l−1 neutral red.
experimental condition as in Fig. 1. Other experimental condition as in Fig. 1.

results are tabulated with those determined by
other methods (see Table 1).
3.3. Equilibrium time of neutral red in surfactant
solution
When the concentration of surfactant is less
than the CMC, the voltammetric curve does not
change with increasing equilibration time of the
neutral red–surfactant solution before determina-
tion. At concentrations approximately equal to, or
greater than the CMC, the peak current of neutral
red decreases with increasing equilibration time,
then plateaus at a constant value (see Fig. 3). The
equilibrium time for CTAB is 18 h and that for
SDS is 16 h. This means that neutral red needs
some time to attain equilibrium concentrations
inside and outside the micelle. In order to get a
reliable analytical result, we selected 24 h as the
steady time for the probe–surfactants solution.
3.4. Adsorptive voltammetric characteristic of
neutral red –surfactant systems
When the concentration of surfactant is below
the first CMC, that of neutral red is fixed. With
an increase of pre-accumulation time (t ), i of
a p
neutral red first increases then plateaus. This means
that the adsorption–desorption balance is set up
(see Fig. 4). If the concentration of neutral red
increases or decreases, the t value of balance
a
changes similarly. The peak current varies linearly
with the potential scan rate. These phenomena
suggest that the reactant is adsorbed on the

Table 1
The first CMC and second CMC values determined by various methods

1st CMC (mmol l−1) Method 2nd CMC (mmol l−1) Method

SDS 8.3 Conductivity [2] 65 Conductivity [2]

SDS 8.0–8.5 Viscosity [3] 65–70 Viscosity [3]
SDS 8.3 Light-scattering [4] 70 Light-scattering [4]
SDS 8 Cyclic voltammetry without probe [9] 56 Cyclic voltammetry without probe [9]
SDS 8.3 Adsorptive voltammetry 63 Adsorptive voltammetry

CTAB 0.6 Cyclic voltammetry with probe [7] 6.2 Fluorescence [6 ]

CTAB 0.88 Adsorptive voltammetry 7.0 Adsorptive voltammetry
 C. Ma et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 143 (1998) 89–94
electrode surface. Fig. 2 shows that when the con-
centration of surfactants is lower than the first
CMC, the surfactant concentration does not influ-
ence i . This indicates that CTAB and SDS do not
p 8.146
adsorb on the hanging mercury drop electrode and
hence do not affect the adsorption of neutral red.
3.5. Mechanism of the electrochemical reaction
The overall electrode process in adsorption vol-
tammetry can be divided into two steps.
Adsorption accumulation of neutral red:
NR=NR(ads)
Reduction of the adsorbed reactant:
NR(ads)+neR∞
NR, NR∞ are the oxidative and reductive state of
neutral red respectively. n is the number of
electrons required by the reduction of one neutral
red molecule.
The electronic transfer number of the neutral
red was obtained from
Q=mnF
where m is the molar number of the electro-active
substance, n is the electronic transfer number, and
F is the faraday (96 487 C ). For solution:
Q=cVnF
where c is the concentration of electroactive
species, V is the volume of the solution, so
n=Q/cVF
Prior to adding the neutral red, the potential is
set to the desired electrolysis potential; compensa-
tion controls are used to ‘‘zero’’ the integrator,
thus canceling any background current. The neut-
ral red is then added and the subsequent electroly-
sis performed. When the measured cell current
equals that before the sample was added, the
endpoint can be considered to have been reached.
The results determined by this method are shown
in Table 2.
The electronic transfer number of the single
neutral red molecule obtained by the coulomb
method is 2 for both systems. So Eq. (2) can be
written as NR(ads)+2eNR∞.
93
Table 2
Results determined by the coulomb method
Q a (×10−3 C ) c (mmol l−1) V (ml ) F (C ) n
0.2 0.2 96487 2.1 (SDS )
8.476 0.2 0.2 96487 2.2 (CTAB)
a Average value of three determinations.
3.6. Distribute ratio of neutral red inside and
outside the micelle
(1) As shown above, neither micelle nor monomer
SDS or CTAB can be adsorbed onto the HMDE
surface, thus neutral red molecules inside the
(2) micelle do not take part in the electrode reaction.
This is supported by the observation that, at
concentrations above and below the CMC, the
shape of the reduction peak is unchanged. So only
the neutral red outside the micelle can participate
in the reaction and obey the above reaction mecha-
nism. Thus the distribution ratio of neutral red
inside and outside the micelle is estimated as
(3) follows: N represents the molar number of neutral
in
red inside the micelle, Nout represents the molar
number outside the micelle. The ratio is
N /N =(i −i )/i . As the concentration of
in out p max p p
neutral red is fixed, i represents the maximal
(3∞) p max
peak current at all concentration of surfactants
and i is the peak current at a certain concen-
p
tration. At the second CMC of the two surfactants,
the distribution ratio of neutral red is 2.3 for SDS
(4) and 4.7 for CTAB. This indicates that the solubility
of the probe in the CTAB rod-shaped micelle is
greater than that in the SDS micelle. The above
phenomenon may be caused by the fact that the
second CMC of CTAB is lower than that of SDS.
This conclusion is similar to that drawn from the
first CMC of surfactants [14].
Acknowledgment
This work was supported by the Fund of
Chinese National Natural Science and Open
Laboratory of Photographic Chemistry Institute,
Academia Sinica.
94 C. Ma et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 143 (1998) 89–94
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