COLLOIDS

AND
ELSEVIER

Colloids and Surfaces

A: Physicochemical and Engineering Aspects 125 (1997) 221 224

SURFACES

Spectrophotometric and conductimetric determination of the

critical micellar concentration of sodium dodecyl sulfate and
cetyltrimethylammonium bromide micellar systems modified by
alcohols and salts
I. Benito, M.A. Garcia, C. Monge, J.M. Saz *, M.L. Marina
Departamento de Quimica Analltica, Facultad de Cieneias, Universidad de Alcald de Henares, 28871 Alcald de Henares,

(Madrid), Spain
Received 5 August 1996; accepted 15 January 1997

Abstract

Determination of the critical micellar concentration of some modified micellar systems used as mobile phases in
micellar liquid chromatography and micellar electrokinetic chromatography has been achieved. Sodium dodecyl
sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) were used as surfactants, n-propanol and n-butanol as
modifiers, and phosphate buffer was included in some of the micellar systems. 1997 Elsevier Science B.V.

Keywords: Surfactants; Micelles; Micellar systems; Sodium dodecyl sulfate (SDS); Cetyltrimethylammonium bromide
(STAB); Critical micellar concentration

1. Introduction

Micellar systems are used to increase the solubility of organic compounds in aqueous media [1 ],
to separate simultaneously ionic and non-ionic
species by chromatographic techniques [2,3] and
to improve sensitivity in spectrophotometric
determinations [4-6], among other features of
analytical concern. Due to the large number of
applications in analytical chemistry for micellar
systems, their characterization has become an
usual task for many laboratories.
Micellar systems arise when surfactant monomers group into aggregates, whose shape and size
depend on the nature and concentration of other
species in solution [7-9]. The concentration of
* Corresponding author. Fax: +34 1 885 4971.
0927-7757/97/$17.00 1997 Elsevier Science B.V. All rights reserved
PII S0927-7757 (97)00014-9

surfactant needed to initiate micelle formation is

called the CMC (critical micellar concentration).
The CMC can be determined by conductimetric
[ 10-13], spectrophotometric [ 14-20], surface tension measurement [21], fluorimetric [22] and light
scattering [23] methods, among others.
The use of micellar systems in high performance
liquid chromatography and capillary electrophoresis has given rise to micellar liquid chromatography
( M L C ) [24] and micellar electrokinetic chromatography ( M E K C ) [25], respectively. In these
techniques, CMC is necessary to predict solute
retention (and hence the separation selectivity)
[26], as an example.
In this work, the CMC of some micellar systems
largely used as mobile phases in M L C and M E K C
are presented, The effect on this parameter of some
additives (e.g. n-propanol, n-butanol and buffers)

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I. Benito et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 125 (1997) 221-224

which are generally used in the mobile phase in

MLC and M E K C is also studied.

1600
1400
09

1200
1000

2. Experimental procedure
,w

800

2.1. Micellar systems

o
-~
-o
c-

600

Sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) were used as
surfactants, and n-propanol (n-PrOH) or n-butanol (n-BuOH) (at a 3-10% v/v) as cosurfactants.
Sodium phosphate buffer (PB) (0.01M, pH = 6.9)
was also used in some of the micellar systems.

400

200
0

0,005 0,01 0,015 0,02 0,025 0,03

[SDS] (M)

2.2. Conductimetric measurements

0,5
Conductimetric determination of the CMC was
carried out through the change in the slope when
the specific conductivity versus surfactant
concentration for surfactant solutions is plotted
(Fig. 1(a)). The straight lines showed in Fig. 1 (a)
were obtained by the least square procedure using
the first and the last four points, respectively. The
CMC values were determined by the intersection
of these lines. Data showed in Table 1 are the
average of at least three different experiments in
each case. The CTAB and SDS concentrations
ranged from l0 -4 to 2.5 x 10 -3 M, and 10 . 3 to
2.5 x 10 -2 M, respectively.
2.3. Spectrophotometric measurements

When the alcohol concentration is large [ 11 ], or

a buffer is added, the change in the slope at the
conductimetric plots is too small to be determined
accurately. In this case, a spectrophotometric
method was used to determine the CMC value
[15]. This determination was based on the shift
that the UV-Vis absorption spectrum of a dye
experiences in the micellar medium [ 14,19]. Methyl
orange and pinacyanol chloride were used as dyes
for SDS and CTAB, respectively. CMC values
were determined through the change in the slope
when the absorbance versus surfactant concentration is plotted, at 430 and 607 nm for SDS and
CTAB, respectively (Fig. l(b)). Data showed in
Table 1 are the average of at least three different

1 b) 3% n-PrOH.

0,4
O

o
t-t~

0,3
0,2

o
.~

<

0,1

#
t

0,005 0,01 0,015 0,02 0,025 0,03

[SDS] (M)

Fig. 1. Specific conductivity (a) and absorbance (b)

surfactant concentration for SDS + 3% (v/v) n-PrOH.

vs

experiments in each case. The concentration

range was 6 x 1 0 - 5 to 3 x 1 0 - 3 M and 10-4 to
2.6x 10-2M for CTAB and SDS, respectively.
The concentration of methyl orange and pinacyanol chloride was 10 -5 M and 2.5 x 10 .6 M,
respectively.
2.4. Reagents

All reagents were of analytical grade. SDS,

CTAB, n-PrOH, n-BuOH, NaH2PO 4 x 7H20 and
NaOH were obtained from Merck, pinacyanol
chloride from Sigma and methyl orange from
Panreac. Solutions were prepared in deionized
water.

I. Benito et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 125 (1997) 221-224

223

Table 1
CMC

values for S D S a n d C T A B systems in m o l a r i t y u n i t s ( M ) d e t e r m i n e d by c o n d u c t i m e t r i c ( C M ) a n d s p e c t r o p h o t o m e t r i c ( S M )

m e t h o d s a t 298 K
% Alcohol

n-PrOH

n-BuOH

CM

SM

CM

SM

n-PrOH + PB

n-BuOH + PB

CM

CM

SM

SM

SDS
0

8 . 0 1 0 -3

8 . 0 10 - 3

8 . 0 x 10 - 3

8 . 0 10 - 3

--

5 . 0 10 - 3

--

5 . 0 x 10 - 3

8.110

8.010-3

7.9x10

5.010-3

__

3.010-3

__

5.010-3

7.110

3.0x10-3

7.5

10

CTAB
0

7.010-3
.

__
.

--

3.5

10

-3

3.5x10

2.510

__

1.8

__

--

---

1.5 X 10 - 3
x

10

--

9.5 10 - 4

--

9.5 x 10 4

3.0 10 4

__

8.5 x 10 - 4

9.0 10 - 4

--

5.0 10 - 4

--

2.5 10 - 4

--

1.0 10 - 4

8.3 10 - 4

7.0 10 - 4

--

2.3 10 - 4

--

1.8 10 - 4

--

1.2 10 - 4

5.5 10 - 4

--

2.5 10 - 4

--

1.8 10 - 4

--

--

3.5 x 10 - 4

--

--

--

1.4 x 10 - 4

--

--

7.5
10

2.5. Apparatus
For
conductimetric
measurements,
a
CRISON-524 conductimeter with a conductivity
cell formed by two platinum electrodes
(c= 1 cm -1_+5%) was used. Solutions were thermostated at 298 K using a B.BRAUN-4P bath
and B.BRAUN-Thermomix BU thermic head. A
Perkin-Elmer Lambda 5 spectrophotometer was
used for spectrophotometric measurements.

3. Results and discussion

Good agreement between CMC values obtained

through conductimetric and spectrophotometric
methods is observed in Table 1. As a result, a
spectrophotometric method was used when it was
not possible to use conductimetric techniques.
3.1. Effect of the nature and concentration of
alcohol on the CMC
The results shown in Table 1 indicate that: (i)
CMC decreases as an alcohol is present in solution,
and (ii) when the alkyl chain of the alcohol
increases, the decrease in CMC is more pronounced. These results are similar to those
reported by other authors [12].

3.0 10 - 4

At first, the decrease in CMC by alcohols is not

obvious, since the surfactant solubility in water
is increased by alcohols. In fact, it has been
reported that CMC increases when the alcohol
concentration is high [ 11 ].
The free energy of transfer of a n-alkyl alcohol
from pure liquid to water is positive, in spite of
the negative value of the enthalpy [27]. So, the
enthalpic decrease is counteracted by an entropic
decrease [28]. In a micellar medium, the entropic
decrease originated by the alcohol molecules in
water may be counteracted by the transfer of
alcohol and surfactant molecules from the aqueous
to the micellar phase, explaining thus the decrease
in the CMC.
The significance of the entropic factor on the
CMC attributed to the alcohol has been demonstrated by the addition of urea to micellar solutions. Urea increases the entropy of the system by
breaking the hydrogen bonds between water molecules, and this effect is joined to an increase in
CMC [11].
A second factor may explain CMC decrease by
alcohols. Alcohol molecules in the micellar phase
are positioned with their alkyl chain toward the
micellar core, while their hydroxyl groups are
located between the ionic heads of surfactant molecules, thus increasing the length between them

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I. Benito et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 125 (1997) 221-224

which decreases repulsions [12]. This factor

contributes to the micelle stability, therefore
decreasing the CMC.
3.2. Effect of the ionic strength on the CMC

As other authors have depicted [16,21 ], electrolytes decrease CMC (Table 1). The ions of a salt
neutralize the charge at the micelle surface decreasing the thickness of the ionic atmosphere around
the surfactant ionic heads, and the electrostatic
repulsions between them, helping in this way to
the micellization process [21].

Acknowledgment
The authors thank DGICYT (Spain) for project
PS90-0026. They also thank C. Marina for
linguistic assistance.

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