Journal of Colloid and Interface Science 286 (2005) 747–754

www.elsevier.com/locate/jcis

Effect of glycerol on micelle formation by ionic and

nonionic surfactants at 25 ◦C
Gerardino D’Errico ∗ , Donato Ciccarelli, Ornella Ortona
Chemistry Department of Naples University “Federico II,” Via Cintia, Complesso di Montesantangelo, I-80126 Naples, Italy
Received 14 October 2004; accepted 21 January 2005
Available online 2 March 2005

Abstract
The effect of glycerol on the micellization of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and of the ethoxylated
nonionic surfactant Brij 58 has been investigated by various experimental techniques. For both surfactants the critical micellar concentration
(cmc), determined by surface tension measurements, is almost unaffected by the presence of glycerol in the mixture; only at high glycerol
concentrations (
20% w/w) does the cmc significantly increase. The area per surfactant molecule at the air–solution interface, A, increases
with increasing glycerol weight percentage, wg . Fluorescence quenching measurements indicate that the presence of glycerol induces a
lowering of the aggregation number of both surfactants. The glycerol intradiffusion coefficient has been measured by the pulsed-gradient
spin–echo NMR technique as a function of glycerol content at constant surfactant concentration. It is almost unaffected by the presence
of the surfactants, indicating that no direct glycerol–surfactant interaction occurs in the mixture. The surfactant intradiffusion coefficient
has been also measured. In the case of CTAB, it increases with increasing glycerol concentration, a reflection of the decreased aggregation
number. For Brij 58, in spite of the lowering of the aggregation number, the surfactant intradiffusion coefficient decreases with increasing
glycerol concentration, suggesting an increase of the intermicellar interaction. The experimental evidence shows that for both surfactants the
micellization is affected by the presence of glycerol through an indirect, solvent-mediated mechanism. In the case of CTAB, the main effect
of glycerol is a lowering of the medium dielectric constant, which enhances the electrostatic interactions in solution. In the case of Brij 58,
the results can be interpreted in terms of a salting-out effect according to which glycerol competes with the surfactant for water molecules,
causing a dehydration of the surfactant ethoxylic headgroup.
 2005 Elsevier Inc. All rights reserved.

Keywords: Micellization; Glycerol; Surface tension; Fluorescence quenching; Intradiffusion

1. Introduction glycerol on the delicate balance of hydrophilic/hydrophobic

Characterization of surfactants’ self-aggregation in glyc-
erol aqueous mixtures is important from a technological
as well as a basic viewpoint. Glycerol and surfactants are
simultaneously present in many pharmaceutical and cos-
metic products; in such formulations, surfactants are em-
ployed as carriers of active materials, while glycerol is added
in order to improve the sensory perception (e.g., viscosity,
sweetness) [1]. At the same time, analysis of the effect of
* Corresponding author. Fax: +39-081-674090.
E-mail address: derrico@chemistry.unina.it (G. D’Errico).
0021-9797/$ – see front matter  2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.01.030
interactions that determine surfactant micellization could
help the comprehension of more complicated processes in
which similar effects are important. As an example, glyc-
erol is extremely effective in the protection of enzymes
against the denaturing effects of urea [2] and temperature
changes [3].
Various papers have been published concerning the
physicochemical characterization of surfactants’ micelliza-
tion in aqueous glycerol mixtures. Initially, most of them
dealt with ionic surfactants [4–8]; more recently, nonionic
surfactants [9] and amphiphilic block copolymers have also
been considered [10,11]. The extent of glycerol effects, and
748 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754
the mechanism through which they are supposed to act, de-
pend on the considered surfactant.
In the present paper, we report the results of an ex-
perimental investigation on the effects of glycerol on the
micellization of a cationic surfactant, cetyltrimethylammo-
nium bromide (CTAB), and a nonionic ethoxylated surfac-
tant, Brij 58. The systems water–glycerol–CTAB and water–
glycerol–Brij 58 have been studied by various experimen-
tal techniques, analyzing the changes in the surfactant self-
aggregation as a function of the glycerol concentration in
the system. Surface tension measurements have made it pos-
sible to determine the surfactants’ critical micelle concen-
tration, cmc, and the area at the air–solution interface per
surfactant molecule, A. Measurements of static fluorescence
quenching have furnished the surfactants’ mean aggrega-
tion number, N . Intradiffusion coefficients, obtained by the
pulsed-gradient spin–echo (PGSE) NMR technique, have
given information on the hydrodynamic dimensions of the
micellar aggregates. The combined analysis of the experi-
mental results obtained by these techniques allows a detailed
description of the surfactants’ behavior in the presence of
glycerol.
The report is organized as follows: in Section 3 the results
obtained for the two surfactants are presented separately; in
Section 4, the findings for the two considered surfactants are
discussed and compared, in the attempt to achieve a general
comprehension of the mechanism through which glycerol af-
fects surfactant micellization.
2. Experimental
2.1. Materials
Cetyltrimethylammonium bromide (n-hexadecyltrimeth-
ylammonium bromide, CH3 (CH2 )15 N(CH3 )3 Br, CTAB), a
Fluka product with purity > 98%, was used without further
purification.
Brij 58 was purchased from Sigma and used without fur-
ther purification. Brij is a registered trademark of ICI Sur-
factants. Brij products present a monodisperse alkyl tail and
a polydisperse ethoxylic head. The mean molecular formula
of Brij 58 is CH3 (CH2 )15 (OCH2 CH2 )20 OH, C16 E20 .
Glycerol, a Sigma product with purity > 99%, was used
without further purification.
Both the fluorescent molecular probe pyrene (Sigma
product, purity > 99%) and the fluorescent quencher cetyl-
pyridinium bromide (Aldrich product, purity > 98%) were
used without further purification.
Twice distilled and degassed water was used as a sol-
vent for surface tension and fluorescence quenching mea-
surements. Heavy water (Sigma product, purity > 99%) was
used as a solvent for PGSE-NMR measurements. All solu-
tions were prepared by weight.
All the experimental data are available by request to the
authors.
2.2. Tensiometry
The surface tension, γ , was measured by the De Nouy
ring method using a KSV Sigma 70 digital tensiometer
equipped with an automatic device to set the time between
two consecutive measurements and to select the rising ve-
locity of the platinum ring. Care has to be taken in using
the De Nouy ring method to deduce surfactant properties,
because the surfactant adsorption kinetics can influence the
results [12]. In our experiments the ring rinsing velocity
was chosen low enough to allow the surfactant adsorption
to reach equilibrium. For the binary system water–glycerol,
measurements were performed using independently pre-
pared mixtures covering the whole composition range. For
the binary systems water–CTAB and water–Brij 58, weighed
amounts of a surfactant solution at a concentration well
above its cmc were added into a weighed amount of water
in the tensiometer circular vessel, thermostatted at 25.00 ±
0.01 ◦ C.
In the case of the ternary systems water–glycerol–CTAB
and water–glycerol–Brij 58, both the titrating and titrated so-
lutions presented the same glycerol weight percent, wg , so
that it remained constant in the measurement vessel during
the titrating procedure. For each surfactant, titrations were
made at different wg , ranging from 2 to 30% w/w.
2.3. Fluorescence quenching
The CTAB and Brij 58 aggregation numbers, N , both
in water and in glycerol aqueous solution, were deter-
mined by analyzing the reduction of the pyrene fluores-
cence due to the presence of cetylpyridinium bromide
acting as quencher [13]. The variation of the pyrene flu-
orescence spectrum was investigated by a Model FP-750
Jasco spectrofluorimeter using an excitation wavelength of
290 nm. For the binary systems water–CTAB and water–
Brij 58, an aqueous solution containing the surfactant at
a molality well above its cmc, the quencher, and pyrene
(2 × 10−6 mol dm−3 ) was initially put into the spectroflu-
orimetric cuvette, thermostatted at 25.0 ± 0.1 ◦ C. Weighed
amounts of a solution containing the same components, at
the same concentration, except the quencher, were subse-
quently added, the pyrene fluorescence spectra being regis-
tered after each addition.
According to the Tachiya model [14], a simple relation
applies between the pyrene fluorescence intensities at a fixed
wavelength with and without the quencher, I and I0 , respec-
tively, and the quencher molar concentration, [Q],


I = I0 exp −[Q]/[M] , (1)
where [M] is the micelle molar concentration. The surfactant
stoichiometric concentration, C0 , and [M] are related by the
equation
[M] = (C0 − Cmon )/N, (2)
 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754 749

where Cmon is the molar concentration of the free monomer The experimental uncertainties in the intradiffusion coeffi-
and N is the mean aggregation number of the micelles. By cients were generally less than 3%.
using Eqs. (1) and (2) and on the reasonable hypothesis that For the ternary systems water–glycerol–CTAB and water–
Cmon ∼= cmc, N/(C0 − cmc) is the slope of the straight line glycerol–Brij 58, measurements were performed at constant
obtained reporting ln(I0 /I ) as a function of [Q]. Thus the fit surfactant molality (0.05 mol kg−1 ) and at a glycerol weight
of Eqs. (1) and (2) to the experimental ln(I0 /I ) values al- percent ranging from 0.5 to 4% w/w. Higher wg were not
lows the determination of the mean aggregation number, N . considered for two reasons: (i) the glycerol NMR signals
Since all the considered solutions were sufficiently diluted, would make the determination of the surfactant diffusion
the surfactant molalities were used instead of the molar con- coefficient more difficult and uncertain; (ii) the viscosity in-
centrations. crease of the solution would make the interpretation of the
In the case of the ternary systems water–glycerol–CTAB experimental data in terms of hydrodynamic dimension of
and water–glycerol–Brij 58, experiments were performed the diffusion particles less reliable.
following the same procedure, with the further condition
of having the same glycerol weight percent, wg , in both
the titrating and titrated solutions. For each surfactant, a 3. Results
set of titrations were made at constant surfactant molality
(0.05 mol kg−1 ) and at wg ranging from 1 to 30% w/w. The 3.1. Ternary system: water–glycerol–CTAB
uncertainty in the N values, evaluated by repeating the mea-
surements several times for selected systems, is ∼10%. The surface tension data for the binary system water–
CTAB, reported as a function of the surfactant molality, m,
2.4. PGSE-NMR are shown in Fig. 1 on a semilogarithmic scale. With increas-
ing m, the surface tension, γ , decreases; as the cmc (1.0 ×
The intradiffusion coefficients of glycerol, Dg , and sur- 10−3 mol kg−1 ) is reached, the curve changes its slope and
factants, Ds , in the systems heavy water–glycerol–CTAB approaches a constant value, γcmc = 36.0 mN m−1 .
and heavy water–glycerol–Brij 58 were determined by the The area at the air–solution interface per surfactant mole-
FT-PGSE NMR technique [15], employing a Varian FT80 cule at the cmc, A, was estimated through the relation [17]
1 H NMR spectrometer with an internal deuterium lock. The
   −1
spectrometer was equipped with a pulsed magnetic field 1 1 ∂γ
A=− , (4)
gradient unit, made by Stelar (Mede, Italy). The tempera- NA qRT ∂ ln m T ,p
ture was controlled at 25.0 ± 0.1 ◦ C with a Stelar variable
where NA is the Avogadro number, R is the gas constant,
temperature controller, Model VTC87. The individual spin–
and T is the temperature. The factor q depends on the sur-
echo peak amplitude, a, for a considered line is given by the
factant type; its value is 1 for most nonionic and zwitterionic
equation
surfactants, while it is 2 for most 1:1 ionic surfactants [18].
  
δ The surface tension derivative at the cmc was evaluated by
a = a0 exp −γgm g Dδ  −
2 2 2
, (3) differentiating a polynomial equation fitted to the premi-
3
cellar data. For CTAB, the measured interfacial area was
where a0 is a constant for a given set of experimental con-
A = (43 ± 2) Å. The cmc, γcmc , and A values obtained in
ditions, γgm is the gyromagnetic ratio of the proton, g is the
the present study are in very good agreement with literature
strength of the applied gradient, and  and δ are the spac-
ing and the length of the gradient pulses, respectively. Echo
delays were kept fixed so that the effects of relaxation were
constant and need not be taken into consideration. The dura-
tion of the two gradient pulses, δ, was varied over a suitable
range to observe the decay of the spin–echo signal. For glyc-
erol the signal amplitude for the protons of the CH2 of the
alkyl tails was followed (chemical shift = 3.7). For CTAB
and Brij 58 the signal amplitude for the protons of the CH2
of the alkyl tails was followed (chemical shift = 1.3). The in-
tradiffusion coefficients of glycerol and surfactant, denoted
as Dg and Ds , respectively, were obtained by applying a non-
linear least-squares routine to the decay of a as a function
of δ. In order to evaluate the values of the intradiffusion co-
efficients, g must be known. Measurements to establish its
value were performed on a reference sample with known Fig. 1. Surface tension vs surfactant molality at 25 ◦ C. Water–glycerol–
intradiffusion coefficient; we used heavy water with trace CTAB mixtures: (!) 0% w/w glycerol; (P) 30% w/w glycerol. Water–
amounts of light water (DHDO = 1.872 × 10−9 m2 s−1 [16]). glycerol–Brij 58 mixtures: (") 0% w/w glycerol; (Q) 30% w/w glycerol.
750 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754

Fig. 2. Water–glycerol mixtures: (1) surface tension and (2) viscosity vs

glycerol weight percent at 25 ◦ C. Fig. 3. Surfactant critical micellar concentration in glycerol aqueous mix-
tures, relative to that in water, as a function of the glycerol weight percent
at 25 ◦ C. (!) Water–glycerol–CTAB mixtures; (") water–glycerol–Brij 58
Table 1
mixtures.
Surfactant critical micellar concentration, equilibrium surface tension of
micellar solutions and area at the air–solution interface per surfactant mole-
cule in the ternary systems water–glycerol–CTAB and water–glycerol–Brij Table 2
58 at 25 ◦ C, as evaluated by surface tension measurements Surfactant aggregation number in the ternary systems water–glycerol–
CTAB and water–glycerol–Brij 58 at 25 ◦ C, as evaluated by fluorescence
wg (% w/w) cmc (mol kg−1 ) γcmc (mN m−1 ) A (Å2 )
quenching measurements
Water–glycerol–CTAB
wg (% w/w) N
0 1.0 × 10−3 36.0 ± 0.1 43 ± 2
2 1.0 × 10−6 36.2 ± 0.2 47 ± 3 Water–glycerol–CTAB
5 1.0 × 10−6 35.8 ± 0.3 51 ± 3 0 72
10 1.0 × 10−6 36.3 ± 0.2 56 ± 4 1 70
15 1.0 × 10−6 36.0 ± 0.3 65 ± 5 2 64
20 1.0 × 10−6 36.3 ± 0.1 78 ± 9 5 60
30 1.5 × 10−6 36.2 ± 0.3 90 ± 15 10 50
20 48
Water–glycerol–Brij 58 30 42
0 6.0 × 10−6 41.2 ± 0.1 54 ± 1
Water–glycerol–Brij 58
2 6.0 × 10−6 40.9 ± 0.2 61 ± 2
0 93
5 6.0 × 10−6 41.0 ± 0.2 67 ± 3
1 78
10 6.5 × 10−6 40.7 ± 0.2 76 ± 4
2 74
15 7.0 × 10−6 40.9 ± 0.1 83 ± 7 5 66
20 10.0 × 10−6 40.0 ± 0.4 89 ± 10 10 57
30 40.0 × 10−6 39.5 ± 0.2 120 ± 20 20 51
30 45

values, obtained using a drop-volume instrument, thus con-

firming the reliability of our experimental approach [18].
The measurements for the ternary mixtures water–glyc-
erol–CTAB, performed at constant glycerol weight percent,
wg , present similar γ trends. The data of the tensiometric
titration with wg = 30% w/w are reported as examples in
Fig. 1. At low m the data of the ternary mixtures are slightly
lower than those of the binary system; the difference tends
to decrease with increasing m. This evidence is due to mild
surface activity of glycerol, as confirmed by inspection of
Fig. 2, in which surface tension data for the binary system
water–glycerol are reported. These experimental data are in
very good agreement with literature data obtained by the
capillary tube method [19], further confirming the reliabil-
ity of our experimental approach.
Similarly to what is observed for the binary system
water–CTAB, and also for the ternary system water–glyc-
erol–CTAB, a constant γcmc value is reached above the
cmc, and an A value was computed from the slope of the
γ trend, as described for the binary system. Inspection of
Table 1 shows that the CTAB cmc is not affected by the
presence of glycerol in the mixtures; see also Fig. 3; only
for wg
30% w/w does the cmc seem to increase slightly.
Analogously, the γcmc is constant; in contrast, the A values
increase with the wg value, indicating a less dense packing
of the surfactant molecules at the air–solution interface.
The mean aggregation numbers, N , of CTAB in water
and in glycerol aqueous mixtures, determined by fluores-
cence quenching experiments, are collected in Table 2. The
datum of the binary system is in good agreement with liter-
ature data [20,21]. N decreases with increasing wg . In these
conditions, a decrease of the hydrodynamic dimension of the
aggregates is expected, which in turn should cause an in-
crease of the aggregates’ intradiffusion coefficient. This is
confirmed by the experimental CTAB intradiffusion coeffi-
 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754 751

Table 3
Surfactant and glycerol intradiffusion coefficients in the ternary systems
water–glycerol–CTAB and water–glycerol–Brij 58 at 25 ◦ C, as evaluated
by PGSE-NMR measurements
wg (% w/w) Ds × 109 (m2 s−1 ) Dg × 109 (m2 s−1 )
Water–glycerol–CTAB
0 0.033
0.5 0.038 0.84
1 0.040 0.81
2 0.041 0.75
3 0.041 0.73
4 0.043 0.74
Water–glycerol–Brij 58
0 0.035
0.5 0.028 0.81
1 0.026 0.82
Fig. 4. Apparent hydrodynamic radius of surfactants’ aggregates in glycerol
2 0.023 0.73
aqueous mixtures as a function of the glycerol weight percent at 25 ◦ C.
3 0.024 0.74
(!) Water–glycerol–CTAB mixtures; (") water–glycerol–Brij 58 mixtures.
4 0.024 0.70
The surfactant molality is 0.05 mol kg−1 .

cients, Ds , collected in Table 3. Note that the CTAB molality,

in samples for intradiffusion measurements (0.05 mol kg−1 ),
is much higher than the cmc, so that the monomer contribu-
tion can be neglected and the experimental Ds values coin-
cide with those of the micellar aggregates. An indication of
the hydrodynamic dimension of the micellar aggregates can
be obtained using the Stokes–Einstein equation,
kB T
Rapp = , (5)
6πηDs
where kB is the Boltzmann constant and η is the dynamic
viscosity of the glycerol aqueous mixtures in which the ag-
gregate diffuse, which was computed from kinematic viscos-
ity [22] and density data [23] from the literature; see Fig. 2.
The values of the apparent hydrodynamic radius, Rapp , com-
puted through Eq. (5) show, as expected, that the hydrody-
namic dimension of CTAB micelles decreases with increas-
ing glycerol content in the mixture; see Fig. 4. However, as
will be discussed further, Eq. (5) strictly holds for noninter-
acting spherical particles diffusing in a continuous medium.
Various experimental techniques put in evidence that CTAB
forms rodlike-shaped micelles [24]; consequently, the com-
puted Rapp values have to be considered as a qualitative in-
dication of the aggregates’ hydrodynamic dimension rather
than as true geometrical parameters.
The values of the glycerol intradiffusion coefficient, Dg ,
in the ternary system heavy water–glycerol–CTAB are also
reported in Table 3. Inspection of Fig. 5 shows that, within
experimental error, Dg assumes the same values measured in
the binary system heavy water–glycerol [25], indicating that
the glycerol mobility is almost unaffected by the presence of
CTAB in the mixture.
3.2. Ternary system: water–glycerol–Brij 58
The surface tension data for the binary system water–Brij
58, reported as a function of the surfactant molality, m, are
shown in Fig. 1. The slope change in the γ trend allows the
Fig. 5. Glycerol intradiffusion coefficient as a function of the glycerol
weight percent at 25 ◦ C. (!) Water–glycerol–CTAB mixtures; (") water–
glycerol–Brij 58 mixtures. The surfactant molality is 0.05 mol kg−1 . The
dotted line is the trend of glycerol intradiffusion coefficient in the binary
system water–glycerol, as reported in Ref. [22].
estimation of the cmc (6.1×10−6 mol kg−1 ), above which γ
approaches a constant value, γcmc = 41.2 mN m−1 . The area
at the air–solution interface per Brij 58 molecule at the cmc
2
was estimated through Eq. (4), obtaining A = (54 ± 1) Å .
These surface tension data are in good agreement with pre-
vious literature data [26].
The measurements for the ternary mixtures water–glyc-
erol–Brij 58, performed at constant wg , present similar γ
trends; also in this case, at very low m, the data of the ternary
mixtures are slightly lower than those of the binary sys-
tem, because of the surface activity of glycerol. The cmc,
γcmc , and the A values are collected in Table 1. The Brij 58
cmc is only slightly affected by the presence of glycerol in
the mixtures up to wg = 15% w/w; with further increasing
wg , the cmc dramatically increases; see Fig. 3. Inspection
of Table 1 shows also that γcmc is practically constant up to
wg = 15% w/w and at higher wg slightly decreases; A in-
creases with increasing wg .
752 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754
The mean aggregation numbers, N , of Brij 58 in wa-
ter and in glycerol aqueous mixtures, determined by fluo-
rescence quenching experiments, are collected in Table 2.
Similarly to what is observed for CTAB, N decreases with
increasing wg .
The Brij 58 intradiffusion coefficients are collected in
Table 3. In this case, differently from what was observed
for CTAB, Ds decreases with increasing wg . Consequently,
the apparent hydrodynamic radius of the aggregates, com-
puted through Eq. (5), increases; see Fig. 4. However, Eq. (5)
strictly holds for noninteracting spherical particles diffusing
in a continuous medium; in real systems the apparent hy-
drodynamic radius of the aggregates has to be considered as
an index of both particle dimension and interparticle inter-
action. Our experimental evidence for the ternary mixtures
water–glycerol–Brij 58 can be interpreted either in terms of
a real enlargement of the micelles’ dimensions, or in terms
of an increase of the intermicellar interactions. Comparison
with fluorescence quenching data suggests the latter inter-
pretation to be more trustworthy; see Section 4 for further
discussion on this point.
The values of the glycerol intradiffusion coefficient, Dg ,
in the ternary system heavy water–glycerol–Brij 58 are also
collected in Table 3. Similarly to what is observed for CTAB,
Dg is almost unaffected by the presence of Brij 58 in the
mixture; see Fig. 5.
4. Discussion
Two different mechanisms for the action of cosolvents (as
well as of water-soluble cosolutes, both indicated as “addi-
tives” in the discussion below) on the surfactant micelliza-
tion can be hypothesized: an indirect mechanism, whereby
the additive changes the properties of the aqueous medium
surrounding the micelles, and a direct mechanism, whereby
the additive replaces some of the water molecules in the
hydration shell of the solute. In the case of ionic surfac-
tants, the indirect mechanism is generally accepted, espe-
cially if no neat or partial charge is present in the additive
molecule; the main effect of the cosolvent is considered
to be the change of the medium dielectric constant, which
in turn affects the electrostatic interaction in solution [6,7].
This interpretation is very suitable for our experimental ev-
idence on the system water–glycerol–CTAB. The glycerol
dielectric constant (εr = 42.5) is substantially lower than
that of water (εr = 78.5) [27]; consequently, the addition
of glycerol enhances the electrostatic interactions in solu-
tion. This effect opposes ionic surfactants’ self-aggregation,
causing a slight increase of the cmc. Furthermore, the in-
creased repulsion among the CTAB cationic headgroups also
causes an increase of the micellar surface curvature, lead-
ing to the formation of smaller aggregates with lower ag-
gregation numbers. It is worth noting that Di Paola and
Belleau [5], analyzing volumetric and calorimetric data on
the system water–glycerol–nonyltrimethylammonium bro-
mide, concluded that the change of the medium dielec-
tric properties cannot be responsible for the changes in the
surfactant micellization, and other effects, such as direct
glycerol–micelle interaction, should be invoked. However,
these authors gave no convincing experimental evidence for
this interpretation; furthermore, their statement according to
which “the dielectric properties of water–glycerol mixtures
are close to those of water” is questionable, as discussed.
Our experimental evidence excludes any direct glycerol–
CTAB interaction; in fact, if this interaction took place, the
intradiffusion coefficient of glycerol would decrease, since a
fraction of glycerol molecules would diffuse together with
the micellar aggregates. The experimental glycerol diffu-
sion coefficient is almost unaffected by the presence of the
surfactant, thus confirming that no direct glycerol–CTAB in-
teraction takes place.
More controversial is the case of nonionic surfactants, for
which both the indirect and the direct mechanism have been
experimentally put in evidence, depending on the considered
additive. This is especially true for ethoxylated surfactants,
whose ethoxylic headgroups form a thick layer surround-
ing the micellar core. This layer, consisting of hydrated
poly(ethylene glycol) chains, is usually named “palisade”
and presents good solubilizing properties toward a large
number of guest molecules. As an example, some of us,
studying the micellization of penta(ethylene glycol) mono-
hexyl ether (C6 E5 ) in aqueous solutions of urea, methy-
lurea, or dimethylurea, put in evidence the presence of a
large number of additive molecules in the surfactant sol-
vation shell [28]. However, the analysis of our data on the
system water–glycerol–Brij 58 excludes a direct glycerol–
surfactant interaction: similarly to what we found for the
system water–glycerol–CTAB, the glycerol diffusion coef-
ficient is almost unaffected by the presence of Brij 58 in the
mixture.
Consequently, we conclude that the glycerol action is to
modify the properties of the aqueous medium. However, de-
tailing the physical basis of these modifications can be am-
biguous. Many authors have interpreted their experimental
evidence on the basis of the effect of the additive on water
structure; in fact, some additives (e.g., urea) are considered
structure-breakers, decreasing the number of H-bonds in
bulk water, while other additives (e.g., glucose) are consid-
ered structure-makers, increasing the number of H-bonds in
bulk water. The classification of one additive as a structure-
breaker or structure-maker is usually based on the results
of calorimetric and osmotic measurements [29]. According
to this approach, glycerol is considered to be a structure-
maker. Actually, some of us, by analyzing transport proper-
ties of the binary mixtures water–glycerol through the veloc-
ity cross-correlation coefficients’ approach [25], found the
water-structuring effect of glycerol to be extremely weak.
Furthermore, Warner [30] pointed out that the glycerol mole-
cule can adopt a conformation in which the spacing between
the oxygen atoms is compatible with the second nearest
neighbor distance of the oxygen in liquid water, so that wa-
 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754
ter structure should be only slightly affected by the presence
of glycerol molecules. Consequently, interpretation of the
effect of glycerol on surfactant micellization in terms of
glycerol structure-making ability is questionable and other
effects should be looked for.
Aramaki et al. [9] interpreted small-angle X-ray scatter-
ing and PGSE-NMR data on the system water–glycerol–
octa(ethylene glycol) dodecyl ether (C12 E8 ) in terms of
dehydration of the ethylene glycol chains with increasing
glycerol content. According to these authors, this effect is
similar to the salting-out effect exerted by many inorganic
salts: glycerol is a less good solvent than water for ethoxylic
chains at 25 ◦ C, so that not only do glycerol molecules
not enter the solvation shell of the surfactant hydrophilic
heads, but they also compete for water molecules, causing
a dehydration of the ethoxylic chains. This interpretation
seems suitable for our experimental evidence on the sys-
tem water–glycerol–Brij 58: the dehydration of ethoxylic
chains, causing an increase of the intrachain interactions,
leads to their contraction close to the micellar surface, in-
ducing steric repulsions among surfactant headgroups. This
effect reduces the micellization driving force, and conse-
quently the cmc increases. The same effect causes an in-
crease of the curvature of the micelle surface, leading to a
decrease of the surfactant aggregation number. Furthermore,
the reduction of water–ethoxylic chain interaction favors the
intermicellar interactions [31], which reduce the surfactant
intradiffusion coefficient, resulting in a increase of the ap-
parent hydrodynamic radius of the aggregates, as shown
by our experimental evidence. These intermicellar interac-
tions could result, at surfactant concentrations higher than
those considered in the present work, in the formation of
multiconnected micelles [9]. From this point of view, ad-
dition of glycerol to aqueous ethoxylated surfactants seems
to affect the system behavior similarly to a temperature in-
crease [31].
5. Conclusions
The results of the present paper are of interest in both
technological and basic scientific fields. Overall, our exper-
imental evidence indicates that the surfactant micellization
in aqueous medium is not much affected by the presence
of glycerol in the mixture. Indeed, the surfactant cmc does
not change up to a glycerol weight percentage, wg , equal
to 20% w/w; in the same wg range, the surfactant aggre-
gation number decreases by a maximum of 30%. In con-
sideration of the large exploitation of both glycerol and
surfactants in cosmetic and pharmacological formulations,
this conclusion is important, making it possible to easily
predict the behavior of a given surfactant in glycerol aque-
ous mixture from the knowledge of its behavior in wa-
ter.
Furthermore, by combining the results obtained by all the
experimental techniques employed in the present work, it
753
is possible to achieve a good comprehension of the mech-
anism through which glycerol affects the surfactant mi-
cellization. Interestingly, this mechanism has been found
to be similar for ionic and nonionic surfactants. In fact,
the experimental evidence shows that for all surfactants
the micellization is affected by the presence of glycerol
through an indirect, solvent-mediated, mechanism. In the
case of ionic surfactants, the main effect of glycerol is a
lowering of the medium dielectric constant, thus enhanc-
ing the electrostatic interaction in solution. In the case of
nonionic ethoxylated surfactants, the results can be inter-
preted in terms of a salting-out effect, according to which
glycerol competes with surfactants for water molecules,
causing a dehydration of the surfactant ethoxylic head-
groups.
Acknowledgments
This research was carried on with the financial sup-
port of the Italian MIUR-Cofin 2002. We thank Professor
L. Costantino and Professor V. Vitagliano for their helpful
comments.
References
[1] M. Martin, J. Swaebrick, K.P. Ananthapadamanabhan (Eds.), Physical
Pharmacy, Lea & Febiger Press, Philadelphia, PA, 1983.
[2] J. Jarabak, A.E. Seeds, P. Talalay, Biochemistry 5 (1966) 1269.
[3] J. Jarabak, J.A. Adams, H.G. Williams-Ashman, P. Talalay, J. Biol.
Chem. 237 (1962) 345.
[4] M.L. Corrin, W.D. Hrakins, J. Chem. Phys. 14 (1946) 640.
[5] G. Di Paola, B. Belleau, Can. J. Chem. 53 (1975) 3452.
[6] M.S. Bakshi, J. Chem. Soc. Faraday Trans. 89 (1993) 4323.
[7] R. Palepu, H. Gharibi, D.M. Bloor, E. Wyn-Jones, Langmuir 9 (1993)
110.
[8] N. Takisawa, M. Thomason, D.M. Bloor, E. Wyn-Jones, J. Colloid
Interface Sci. 157 (1993) 77.
[9] K. Aramaki, U. Olsson, Y. Yamaguchi, H. Kunieda, Langmuir 15
(1999) 6226.
[10] P. Alexandridis, L. Yang, Macromolecules 33 (2000) 5574.
[11] Y. Lin, P. Alexandridis, J. Phys. Chem. 106 (2002) 12,124.
[12] M. Deleu, M. Paquot, C. Blecker, in: A.T. Hubbard (Ed.), Encyclope-
dia of Surface and Colloid Science, Dekker, New York, 2002, p. 5119.
[13] N.J. Turro, A. Yekta, J. Am. Chem. Soc. 100 (1978) 5951.
[14] M. Tachiya, Chem. Phys. Lett. 33 (1975) 289.
[15] P. Stilbs, Prog. NMR Spectrosc. 19 (1987) 1.
[16] R. Mills, J. Phys. Chem. 77 (1973) 685.
[17] J.W. Gibbs, Collected Works, vol. 1, Yale Univ. Press, New Haven,
CT, 1948.
[18] J. Eastoe, S. Nave, A. Downer, A. Paul, A. Rankin, K. Tribe, J. Pen-
fold, Langmuir 16 (2000) 4511.
[19] R.C. Ernst, C.H. Watkins, H.H. Ruwe, J. Phys. Chem. 40 (1936) 627.
[20] V. Mosquera, J.M. del Río, D. Attwood, M. García, M.N. Jones, G. Pri-
eto, M.J. Suarez, F. Sarmiento, J. Colloid Interface Sci. 206 (1998) 66.
[21] S. Ghosh, J. Colloid Interface Sci. 244 (2001) 128.
[22] P.N. Shankar, M. Kumar, Proc. R. Soc. London Ser. A 444 (1994) 573.
[23] E.C.H. To, J.V. Davies, M. Tucker, P. Westh, C. Trandum, K.S.H. Suh,
Y. Koga, J. Solution Chem. 28 (1999) 1137.
754 G. D’Errico et al. / Journal of Colloid and Interface Science 286 (2005) 747–754

[24] F. Li, J.Z. Li, H.Q. Wang, Q.J. Xue, Colloids Surf. A 127 (1997) 89.
[25] G. D’Errico, O. Ortona, F. Capuano, V. Vitagliano, J. Chem. Eng.
Data 49 (2004) 1665.
[26] M. Abe, N. Tsubaki, K. Ogino, J. Colloid Interface Sci. 107 (1985)
503.
[27] D.R. Lide (Ed.), Handbook of Chemistry and Physics, 72nd ed., CRC
Press, Boca Raton, FL, 1991.
[28] L. Costantino, G. D’Errico, P. Roscigno, V. Vitagliano, J. Phys. Chem.
104 (2000) 7326.
[29] C. Cascella, G. Castronuovo, V. Elia, R. Sartorio, S. Wurzburger,
J. Chem. Soc. Faraday Trans. 1 85 (1989) 3289.
[30] D.T. Warner, Nature 196 (1962) 646.
[31] P.G. Nilsson, H. Wennerström, B. Lindman, J. Phys. Chem. 87 (1983)
1377.