J. Chem.

Thermodynamics 44 (2012) 107–115

Contents lists available at SciVerse ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Aggregation behavior and intermicellar interactions of cationic Gemini

surfactants: Effects of alkyl chain, spacer lengths and temperature
Marjan Hajy Alimohammadi a, Soheila Javadian a,⇑, Hussein Gharibi a, Ali reza Tehrani-Bagha b,
Mohammad Rashidi Alavijeh a, Karim Kakaei c
a
Department of Physical Chemistry, Tarbiat Modares University, P.O. Box 14115-117, Tehran, Iran
b
Institute for Colour Science and Technology, Tehran, Iran
c
Department of Chemistry, Maragheh University, Maragheh, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The aggregation behavior of the cationic Gemini surfactants CmH2m+1N(CH3)2(CH2)S (CH3)2 N CmH2m+1,2Br
Received 29 May 2011 with m = 12, 14 and s = 2, 4 were studied by performing surface tension, electrical conductivity, pulsed field
Received in revised form 2 August 2011 gradient nuclear magnetic resonance (PFG-NMR), and cyclic voltammetry (CV) measurements over the
Accepted 6 August 2011
temperature range 298 K to 323 K. The critical micelle concentration (CMC), surface excess (Umax), mean
Available online 16 August 2011
molecular surface area (Amin), degree of counter ion dissociation (a), and the thermodynamic parameters
of micellization were determined from the surface tension and conductance data. An enthalpy–entropy
Keywords:
compensation effect was observed and all the plots of enthalpy–entropy compensation exhibit excellent
Surface tension
Enthalpy–entropy compensation
linearity. The micellar self-diffusion coefficients (Dm) and intermicellar interaction parameters (kd) were
Thermodynamic obtained from the PFG-NMR and CV measurements. These results are discussed in terms of the intermicel-
Micellization lar interactions, the effects of the chain and spacer lengths on the micellar surface charge density, and the
Gemini surfactants phase transition between spherical and rod geometries. The intermicellar interaction parameters were
Aggregation found to decrease slightly with increasing temperature for 14–4–14, which suggests that the micellar sur-
Intermicellar interaction face charge density decreases with increasing temperature. The mean values of the hydrodynamic radius,
Rh, and the aggregation number, Nagg, of the Gemini surfactants’ m–4–m micelles were calculated from the
micellar self-diffusion coefficient. Moreover, the Nagg values were calculated theoretically. The experimen-
tal values of Nagg increase with increases in the chain length and are in good agreement with both previous
results and our theoretical results.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction factors underlying the variation of their thermodynamic properties

Gemini surfactants are composed of two hydrophobic chains
and two hydrophilic head groups connected by a spacer that can
be hydrophilic or hydrophobic and rigid or flexible [1,2]. These sur-
factants have attracted considerable interest within both academic
and industrial circles over the last decade because Gemini surfac-
tants are superior to the corresponding conventional monomeric
surfactants in a number of aspects. Gemini surfactants have a high-
er surface activity, a lower CMC [3], better solubilizing power [4],
much lower Krafft points [3–5], and better wetting [6], viscoelas-
ticity, gelification, and shear thickening [4] than the corresponding
conventional monomeric surfactants. Owing to their remarkable
properties, considerable effort has been invested in the design
and synthesis of new Gemini surfactants [7–12] to study the rela-
tionship between their molecular structures and their aggregation
morphologies in aqueous solution [13–17] and to examine the
⇑ Corresponding author. Fax: +98 21 82883755.
E-mail addresses: javadian_s@modares.ac.ir, javadians@yahoo.com (S. Javadian).
with the lengths of their chains and spacers [18–28].
There is no doubt that understanding the micellization requires
its complete thermodynamic characterization. The thermodynamic
changes associated with adsorption and micelle formation have
been investigated from the theoretical and experimental view-
points by many research groups.
In the present study, we carried out an investigation of the aggre-
gation behaviors of several Gemini surfactants, including their ther-
modynamics of micellization, adsorption in the air–liquid interface,
the structures of their aggregates, and the variation of their intermi-
cellar interactions with temperature. We used techniques including
surface tension, conductometry, PFG-NMR, and CV. First, the ther-
modynamic properties of micellization were determined by using
CMC and a values. Second, the PFG-NMR and CV measurements en-
abled the investigation of the structures of the surfactants’ aggre-
gates and their intermicellar interactions. Finally, by comparing
the results for these surfactants, we determined not only the effects
of varying the number of carbon atoms of the alkyl chain on the
solution properties of the Gemini surfactants but also the effects

0021-9614/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2011.08.007
108 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115
of varying the hydrophobicity of the spacer chain on micelle forma-
tion. In addition to the determination of the abovementioned micel-
lar parameters, this research demonstrates, for the first time, the
usefulness of CV in the study of the effects of increasing the lengths
of the hydrophobic tail and spacer of Gemini surfactants and those
of varying the temperature on their micellar parameters, intermi-
cellar interactions, and sphere to rod geometry changes.
2. Experimental
2.1. Materials
Gemini surfactants with quaternary ammonium bromide head
groups and linear alkyl tails with the general formula [CmH2m+1–
N+–(CH3)2–(CH2)n–(CH3)2–N+–CmH2m+1]2 Br, where m = 12 and
14 and n = 2 and 4, referred to here as m–n–m, 2 Br surfactants,
were synthesized and purified by the known methods reported
previously [29].
2.1.1. Surface tension measurements
The surface tension measurements were performed with a
Krüss K12 tensiometer by using the ring method [30,31]. The plat-
inum ring was thoroughly cleaned and flame dried before each
measurement. The uncertainty of the measurements was
±0.1 mN  m1. In all cases, more than three successive measure-
ments were carried out, and the standard deviation did not exceed
more than 0.08 mN  m1. The temperature was maintained at a
constant value by circulating the thermostatted water through
the jacketed vessel containing the solution. The temperature con-
trol accuracy was within ±0.1 K.
2.1.2. Electrical conductivity measurements
The measurements of the conductivity of the surfactant solu-
tions were performed with a conductometer, Jenway 4510. After
investigating the conductivity of the solvent, three successive mea-
surements of the conductivity of the surfactant solutions were car-
ried out at a controlled constant temperature. The uncertainty of
the measurements was ±0.01 lS  cm1. The employed conductiv-
ity cell was shown in SM.
2.1.3. NMR measurements
NMR self-diffusion measurements were performed on a Bruker
DRX 500 Avance NMR spectrometer at room temperature. A longi-
tudinal eddy-current delay with a bipolar pulse pair (LEDBPP)
pulse sequence [32] was used to determine the self-diffusion coef-
ficients (D). In this technique, micelle self-diffusion is monitored by
analyzing the signals from trace amounts of tetramethylsilane
(Me4Si) added to the solution, which are assumed to be completely
solubilized in the micellar phase. All NMR measurements were
performed at 25 °C. The basic sequence was used with pulse field
duration, d, of 5 ms and a time interval, D, of 200 ms between gra-
dient pulses.
2.1.4. CV measurements
CV was performed by using an electrochemical analyzer, SAMA
500. A three-electrode system consisting of a working Pt electrode
(the interface at which the redox reaction of interest occurs), a sat-
urated Ag/AgCl reference electrode with a salt bridge containing
3 M aqueous KCl solution (the electrode with a stable potential
against which the potential at the working electrode is measured)
and the counter electrode (a Pt wire through which all the current
required to maintain the redox reaction at the working electrode
flows). The working electrode was polished with slurry of alumina
powder and then washed carefully with distilled water before each
measurement. Ferrocene (0.001 mol  dm3) was used as the
electroactive probe and KCl (0.1 mol  dm3) was used as the sup-
porting electrolyte. Note that this concentration of the electroac-
tive probe does not significantly affect the micellization of the
surfactants and their mixtures [33].
2.1.5. Computational methods
DFT (density functional theory) calculations were carried out
with the Gaussian 98, Revision A.7 (Gaussian, Inc., Pittsburgh PA).
First, geometry optimization was performed at the B3LYP/6-
311+G(d,p) level in the gas phase. PCM (polarizable continuum
model) calculations were then performed at the B3LYP level with
the 6-311+G(d,p) basis set and the gas-phase optimized geome-
tries. The micellar radius was determined as the distance between
the quaternary nitrogen and the farthest H of the terminal methyl
group. The value of Nagg was calculated from this radius and the
volume of the hydrated monomer, as obtained with the PCM by
assuming that the micellar aggregates are spherical.
3. Results and discussion
3.1. The CMC and the thermodynamics of micellization
The CMC values for m–s–m, (m = 12, 14 and s = 2, 4) have been
obtained with conductivity and surface tension measurements;
representative examples for both techniques are shown in figures
SM-1 and SM-2 respectively. The agreement between the CMCs de-
rived from these two methods is satisfactory; note that the CMC
generally depends on the determination method (table 1). As indi-
cated in table 1, the CMC values for 14–2–14 and 14–4–14 are not
strongly dependent on temperature within the range 298 K to
318 K, whereas the CMC values of 12–2–12 and 12–4–12 initially
decrease and then increase as the system temperature increases.
The initial decrease in the CMC is a direct consequence of the de-
crease in the hydrophilicity of the surfactant molecules
[18,19,34]. The increase in temperature also results in an increase
in the breakdown of the structure of the water molecules sur-
rounding the hydrophobic alkyl group, which is unfavorable to
the formation of micelles. As a result, the onset of micellization
tends to occur at higher concentrations as the temperature in-
creases [34]. The value of the CMC decreases with increases in
the hydrophobic chain length of the Gemini surfactants (table 1).
Increasing the spacer length of the Gemini surfactants also results
in increases in the CMC (table 1). These results are in good agree-
ment with those of previous studies [17,21].
According to the Frahm’s Method, the a was calculated from the
ratio of the slopes above and below the CMC in plots of conductiv-
ity against surfactant concentration [35]. The a values are tabu-
lated in table 1 [35]. Frahm’s method is an approximate method
since the contribution of conductivity of micelles above the CMC
is neglected. Then, the a values were calculated for 12–4–12 and
14–4–14 in T = 298 K using Evans’ method (table 1) [36]. As shown
in table 1, the difference of a values calculated by Evans to the
method of Frahm is more than 100%. Consequently, ignoring the
micellar contribution leads to large differences in the a values cal-
culated by two methods. However, use of the Evans method re-
quires knowledge of Nagg, and these are not always available.
As can be seen in table 1, the a increases with increases in the
chain length of the m–n–m Gemini surfactant homologues. This re-
sult indicates that the binding of the bromide counter ions to the
surfactant ammonium heads weakens with increasing hydropho-
bicity. The increases in a (table 1) within the series of surfactants
indicate that increasing the length of the hydrophobic spacer
means that the distance between the charges increases, and as a
result the necessity of partial neutralization by counter ions be-
comes less. Table 1 shows that the a value of each species tends
 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115 109

TABLE 1
CMC, a, interfacial and thermodynamic parameters of micellization of Gemini surfactants at different temperatures

Compound T/k CMCa  104/ CMCb  104/ ab Cmax  106/ Amin/ cCMC/ DHfe/ Tc/K
(mol  dm3) (mol  dm3) (mol  m2) (nm2  molecule1) (mN  m1) (kJ  mol1)
12–2–12 298 8.09 8.40, 8.05c 0.20, 0.13c 1.69 0.98 26.1 34.78 ± 0.01 293.3 ± 0.1
303 7.75 9.09, 9.1c 0.21, 0.13c 1.71 0.97 26.9
308 7.75 9.35, 9.1c 0.23, 0.13c 1.70 0.98 26.9
313 8.42 10.1.10c 0.23, 0.11c 1.63 1.02 26.6
318 9.09 10.9 0.24 1.50 1.11 26.2
12–4–12 298 9.45 10.7 0.24(0.14) 1.58 1.05 36.2 32.09 ± 0.05 290.0 ± 0.3
303 8.70 11.0, 15d 0.27, 0.32d 1.53 1.09 35.4
308 8.93 11.6, 16d 0.29, 0.35d 1.45 1.14 34.9
313 9.45 12.5, 19d 0.31, 0.38d 1.27 1.30 32.1
318 10.7 12.6, 19d 0.34, 0.41d 1.18 1.40 31.6
14–2–14 308 1.47 1.49, 1.9c 0.24, 0.15c 2.23 0.74 27.8 40.40 ± 0.03 304.3 ± 0.1
313 1.47 1.49, 1.9c 0.25, 0.16c 2.19 0.76 27.2
318 1.55 1.77 0.29 1.85 0.90 27.1
323 1.55 1.78 0.31 1.42 1.17 27.2
333 1.62 1.78 0.36 1.07 1.55 25.7
14–4–14 298 1.61 1.46 0.34(0.160) 1.68 0.99 34.1 36.09 ± 0.01 295.9 ± 0.1
303 1.59 1.51 0.35(0.165) 1.64 1.01 32.7
308 1.59 1.72 0.37(0.168) 1.61 1.03 32.3
313 1.59 1.76 0.38(0.171) 1.40 1.18 32.5
318 1.61 1.75 0.40(0.180) 1.24 1.33 32.4

The a values in parentheses were calculated using Evans method.

a
The CMC values obtained from surface tension measurements.
b
The CMC and a values obtained from conductometry measurements.
c
Data taken from reference [18].
d
Data taken from reference [23].
e
The thermodynamic parameters were calculated by using the CMC values obtained from surface tension measurements and a values calculated according to the Frahm’s
Method.
f
These temperatures are below the Kraft temperature of 14–2–14.

to increase with temperature. Note that even though a shallow
minimum is observed in the CMC–temperature curves, the overall
trend in the respective curves is of increases in the CMC with tem-
perature. If the CMC is regarded as reflecting the solubility of the
micelles, a increases with temperature in parallel with the in-
creased solubility of the micelles. The a is determined by various
factors such as the temperature, the electrical potential around
the micelle, the micellar radius, and the dielectric constant of the
medium, etc. [37]. The gross features of counter ion dissociation
or distribution between the kinetic micelle and the bulk solution
can be described with simplified electrostatic models [37], in
which the stabilization of micelles by counter ion binding results
from a balance between the kinetic motion of the ions and the elec-
tric potential on the micellar surface; this balance eventually re-
sults in increases in a with increases in temperature. In other
words, the binding of counter ions (their adsorption onto the
micellar surface) is an exothermic process whereas the electrolytic
dissociation of micelles (the desorption of counter ions) is an endo-
thermic process.
The surface excess {Cmax/(mol  cm2)} is an effective measure
of adsorption at the air/water interface. The concentration of the
surfactant is always greater at the surface than in the bulk. The sur-
face excess (Cmax) and the minimum area per molecule (Amin) were
calculated by using the Gibbs adsorption equation [38,39]. In table
1, it can be seen that the surface excess concentrations, Cmax, of the
Gemini surfactants decrease with increasing temperature. This
behavior arises because thermal motions increase as the tempera-
ture increases.
The surface excess concentration, Cmax, decreases with in-
creases in the spacer length because the surface area per surfactant
molecule occupied by head groups is larger for larger spacers.
Due to hydrophobic interactions between the chains, the mag-
nitude of Cmax is lower for longer hydrophobic chains, suggesting
that the air/water interface is close-packed and therefore that the
orientation of the surfactant molecule at the interface is almost
perpendicular to the interface. As expected, the trend in Amin is in-
verse with temperature (table 1).
The variations of CMC and a with temperature enable us to
analyze the thermodynamic energetics of micelle formation in
water. The collected data for the variations of CMC and a with tem-
perature are given in table 1 and enable us to analyze the thermo-
dynamic energetics of micelle formation in water. First, the
standard Gibbs free energy change upon micelle formation was
examined. By applying mass action law, the Gibbs free energy of
micellization has been derived for general type of ionic surfactant
containing i polar groups of valency zs bonded to j alkyl chains,
with counterions of valency zc as follow [21,40]:
 
1 i
DGmic =ðkJ  mol Þ ¼ RT 1=j þ ð1  aÞ jzs =zc j ln X CMC
j
þ RTði=jjzs =zc jð1  aÞ ln i=jjzs =zc j  ln j=jÞ; ð1Þ
where XCMC and a are the CMC value on the mole fraction scale and
the degree of counterion dissociation respectively. For the dimeric
surfactants (i = j = 2 and jzs j ¼ jzc j ¼ 1), equation (1) becomes:
1
DGmic =ðkJ  mol Þ ¼ RTð1:5  aÞ ln X CMC  ðRT=2Þ ln 2: ð2Þ
The second term in the right hand side of equation (2) is small with
respect to the first one and negligible. The values of DGmic obtained
by using equation (2) are plotted in figure 1. The DGmic values of
these surfactants do not change significantly with increases in tem-
perature. The Gibbs free energy of micellization becomes more neg-
ative with increases in the hydrophobicity of a surfactant, which
means that for the studied surfactants micelle formation is most
facile for 14–2–14.
By applying the Gibbs–Helmholtz equation to equation (2), the
enthalpy of micellization can be obtained [18]. This method is an
easy one, as it only involves CMC and a determinations, but several
110 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115

80

Thermodynamic parameters/kJmol -1
60 a
40

20

-20

-40

-60
295 300 305 310 315 320
T/K
80
Thermodynamic parameters/kJmol-1

60 b
40

20

-20

-40
295 300 305 310 315 320
T/K

60

c
Thermodynamic parameters/kJmol-1

40

20

-20

-40

-60
305 310 315 320 325 330 335
T/K
50
Thermodynamic parameters/kJmol-1

40
30
d
20
10
0
-10
-20 295 300 305 310 315 320
-30
-40
-50
295 300 305 310 315 320
T/K

FIGURE 1. Plot of thermodynamic parameters of micellization (- - - the Gibbs free energy of micellization ðDGmic Þ, — standard enthalpy ðDHmic Þ and    standard entropy
ðT DSmic Þ) of Gemini surfactants: (h) 12–2–12; (⁄) 12–4–12; (D) 14–2–14; (s) 14–4–14 versus temperatures. The thermodynamic parameters were calculated by using the
CMC values obtained from surface tension measurements and a values calculated according to the method of Frahm.

factors that affect DHmic , are not explicitly considered in data treat- accuracy. For example, the use of a small number of data points
ment by Van’t Hoff analysis [21,41]. In the van’t Hoff approach, usually leads to a linear dependence of DGmic =T on 1/T, hence to
DGmic =T versus 1/T is plotted for several temperatures. The quality a single value of DHmic for the temperature range studied. In this
of these plots depends on the number of data points and their work, this problem can be circumvented by fitting the curve with
 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115 111

60

40

20

ΔΗ˚mic/kJmol-1
0

-20

-40

-60

-80
-0.03 0.02 0.07 0.12 0.17 0.22 0.27
ΔS˚mic/kJmol-1K-1

FIGURE 2. Plot of standard enthalpy ðDHmic Þ versus standard entropy ðDSmic Þ, for Gemini surfactants: (h) 12–2–12; (⁄) 12–4–12; (D) 14–2–14; (s) 14–4–14.

TABLE 2
Parameters obtained in the presence of supporting electrolyte for Gemini Surfactants at their respective CMC values

Compound T/K Dma  1011/(m2  S1) Dmb  1011/(m2  S1) Dm  1011 =ðm2 S1 Þ Rh =Å Nagg kd/(dm3  mmol1) (Nagg)th Nagg

12–2–12 298 2.25 1.54 8.86 – – 0.042 – 48c

12–4–12 298 7.61 5.85 11.38 2.153 35 0.025 27 36d,55e
14–2–14 313 – – 9.08 – – 0.028
14–4–14 298 5.38 4.83 9.4 2.606 51 0.026 38
303 6.31 10.7 2.599 50 0.021
308 7.06 11.7 2.678 54 0.019
313 9.32 13.4 2.620 51 0.015
318 11.30 14.2 2.747 59 0.011
a
The diffusion coefficient values obtained from the PFG-NMR technique in the absence of supporting electrolyte (Ctot = 0.019 mol  dm3).
b
The diffusion coefficient values obtained from CV technique in the presence of supporting electrolyte (Ctot = 0.019 mol  dm3).
c
To calculate P, we calculated a0 values using surface tension plots and volume and length values were determined by Tanford equations (the values in parentheses) and
theoretical calculations. The volume and length values obtained by two methods are given in SM.
d
Data taken from reference [24].
e
Data taken from reference [13].

polynomial of higher order to get temperature-dependent DHmic.
More importantly, however, is that there is no provision in the
van’t Hoff equation for factors that are important for micelle for-
mation of ionic surfactants, in particular, the dependence of micel-
lar geometry, aggregation number, surface-charge density, and
hydration of the head group on T [41]. On the other hand, the ef-
fects of T on the above-mentioned micellar parameters are in-
cluded in the direct (i.e., calorimetric) determination of DHmic .
The enthalpy of micellization, DHmic , is dependent on tempera-
ture (figure 1). The temperature dependence of DHmic might be due
to changes in aggregation number (size) and shape [42,43]. Posi-
tive values of DHmic , such as those observed at low temperatures,
are usually attributed to the release of structural water from the
hydration layers around the hydrophobic parts of the surfactant
molecule [44]. It has been suggested [45] that negative DHmic val-
ues are evidence that London-dispersion interactions are a major
force in micellization.
The entropy contribution to the micellization process can be
estimated from the calculated enthalpy and Gibbs free energy val-
ues [21]. From Gibbs free energy relationship, any uncertainty
introduced in the calculation of DHmic will be carried over to
DSmic [41].
It can be seen in figure 1that the absolute value of T DSmic for all
these surfactants decreases with increasing temperature, which
indicates that raising the temperature leads to a reduction in the
entropy or randomness of the system. The comparison of the
enthalpy and entropy terms (see figure 1) suggests the presence
of a mutual relationship in the form of the enthalpy–entropy
compensation phenomenon [43]. The enthalpy–entropy compen-
sation phenomenon has been found for a variety of processes of
small solutes [46], including those of surfactants [47–51].
In general, such compensation phenomena can be described
with a linear relationship of the form [34,52]:
1
DHmic =ðkJ  mol Þ ¼ DHmic þ T C DSmic : ð3Þ
An acceptable linear relationship was obtained in all compensation
plots, as shown in figure 2; these lines have approximately the same
slope but different intercepts at DSmic ¼ 0. Note that the intercept
DHmic gives the enthalpy effect under the condition DSmic ¼ 0. An in-
crease in the value of the intercept DHmic thus corresponds to a de-
crease in the stability of the structure of the micelles. It was found
that the intercept, DHmic , that characterizes the solute–solute inter-
action is dependent on not only the hydrophobic chain length but
also on the length of the spacer group. Our results indicate that
14–2–14 has a larger negative value (DHmic ) than the other surfac-
tants studied here. The micellar stabilities decrease in the order 14–
2–14 > 14–4–14 > 12–2–12 > 12–4–12. The compensation tempera-
tures range approximately 295 K to 304 K for all these surfactants.
3.2. Intermicellar interactions
From a structural point of view, the most important parameters
of a micellar system are the mean micellar aggregation number
and the hydrodynamic radius, which were determined by using
self-diffusion coefficient measurements with PFG-NMR spectros-
copy and CV techniques.
112 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115

16
14
12

10-11Dm/m2.s -1
10
8
6
4
2
0
295 300 305 310 315 320
T/K

FIGURE 3. Self-diffusion coefficient, Dm as a function of temperature in the presence of various concentrations of 14–4–14, 2Br: (⁄) 0.010; (h) 0.015; (D) 0.020 mol  dm3.

0.03

0.025
-1
kd/dm 3mmol

0.02

0.015

0.01

0.005

0
295 300 305 310 315 320
T/K

FIGURE 4. Plot of intermicellar interaction parameter (kd) against temperature in micellar solutions (14–4–14).

1.8
1.7
1.6
1.5
1.4
U(r

1.3
1.2
1.1
1
0.0 1 0.01 2 0.01 4 0.01 6 0.01 8 0.0 2 0.02 2 0.024
kd/ dm3 mmol-1

FIGURE 5. Plot of the micellar interaction energy (U(r)) against intermicellar interaction parameter (kd) in micellar solutions.

The self-diffusion coefficient values obtained with PFG-NMR are not perturb the micelle and that its rates of entrance/exit into the
listed in table 2. The increases in the self-diffusion coefficient are aggregates with fast and reversible electron transfer are at least
mainly due to decreases in the size of the micelles. The low self-dif- comparable to those of the surfactant monomers. The electrochem-
fusion coefficient values of 12–2–12 and 14–2–14 indicate that the istry of ferrocene in non-aqueous, aqueous, and micellar environ-
presence of these Gemini surfactants with short spacers results in ments is described elsewhere [54–58].
the formation of aggregates that are less curved. It was found [13] The cyclic voltammograms for the one- electron oxidation of
in an electron microscopy experiment that a Gemini surfactant with ferrocene (equation (4)) in 12–4–12 at various scan rates for the
s = 2 forms rod-like micelles. Electron micrographs of 12–2–12 solu- potential range 0.0–0.5 V are given in figure SM 3.
tions have found long cylindrical micelles [15,21]. An investigation
Fc () Fcþ þ e : ð4Þ
with cryogenic transmission electron microscopy found that 12–s–
12 surfactants with 4 6 s 6 12 form spheroidal micelles [13]. In CV, the peak current ipa for a redox-active reversible system is
The CV measurements were used to determine the diffusion given by the Randles–Sevcik equation [59]:
coefficients of the micelles and the intermicellar interaction  1
parameters [53]. In the present study, ferrocene was chosen as nF mD 2
ipa ¼ 0:4463FACn ; ð5Þ
the electroactive probe; ferrocene can be used provided that it does RT
 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115
where n is the number of electrons involved in oxidation or reduc-
tion, A is the area of the electrode (A was determined as the method
described in SM), F is Faraday’s constant, R is the gas constant, T is
the absolute temperature, D is the diffusion coefficient of the elec-
troactive (EC) probe, C is the concentration of the EC probe in the
solution, and v is the scan rate. For micellar systems involving an
EC probe completely solubilized in the micelles, the D in equation
(5) corresponds to the micelle diffusion coefficient Dm since the
probe diffuses with the micelles. Hence, from the slope of the ipa
versus v1/2 plot, the Dm values were obtained for various micelle
concentrations; the concentration of ferrocene was fixed at
1  103 mol  dm3. The Dm was found to decrease with decreasing
spacer length for surfactants 12–s–12 and 14–s–14 (table 2), which
is in good agreement with the PFG-NMR data. In CV measurements,
the addition of supporting electrolyte causes a decrease in Dm or
micellar growth due to reduction electrostatic repulsion between
head groups (table 2). These results are in agreement with previous
findings [55].
At concentrations above, but not far from, the CMC micelles
mutually interact; consequently, the calculated values of diffusion
coefficients are lower than that at the CMC. As attenuation of the
mass-transport parameters is a linear function of surfactant con-
centration therefore linear interaction theory (see SM) was used
for calculation of intermicellar interaction parameters [60,61].
Consequently, extrapolation to infinite dilution (to the CMC) yields
mass-transport parameters that are independent of interparticle
interactions
Dm ¼ D0m ½1  kd ðC s  CMCÞ; ð6Þ
where kd is the intermicellar interaction parameter, D0m is the self-
diffusion coefficient in the absence of micellar interaction, CMC is
the critical micelle concentration, and Cs is the surfactant concen-
tration. The representative profiles of Dm versus (Cs-CMC) for 12–
2–12, 12–4–12, 14–4–14, and 14–2–14 (in the presence of support-
ing electrolyte) are shown in figure SM 4. The values of D0m or DCMC
were calculated from the dependence of Dm on surfactant concen-
tration. The results are shown in table 2. These data were used to
calculate the micellar hydrodynamic radius by using the Stokes–
Einstein equation [62–65].
For s = 2, spherical micelles cannot form and the Stokes–Ein-
stein equation is not valid. For a Gemini surfactant with a longer
spacer, the surface area per surfactant molecule occupied by head
groups is larger than for a Gemini surfactant with a shorter spacer,
i.e., there is a smaller packing parameter, which facilitates the for-
mation of spherical rather than worm-like micelles. According to
the experimental data [21], 12–4–12 and 14–4–14 are likely to
form spherical micelles.
The hydrodynamic radius values are shown in table 2. The Rh
values can be used to compute the aggregation number of the mi-
celles. By assuming spherical micelles and neglecting their intrinsic
instability, the aggregation number can be computed. The Nagg val-
ues are collected in table 2, along with the theoretically calculated
aggregation numbers, Nagg,theor, and those obtained with other
techniques. The CV-based Nagg values are in excellent agreement
with the values obtained using other techniques [13,29]. The Nagg
values are dependent on the chain length of the surfactant hydro-
phobic tail in the presence of electrolyte. The increases in Nagg with
increases in the length of the R group are due to increases in the
packing factor, because such increases affect the volume of the
hydrophobic group more than its length (for the same head group).
In addition, the actual diffusion coefficient, D0m , hydrodynamic ra-
dius, Rh, and aggregation numbers, Nagg of the 14–4–14 micelles
are shown for various temperatures in table 2. The results indicate
an increase in D0m with increasing temperature. At least part of this
change in D0m is due to the decrease in solvent viscosity (see the
113
supporting material). Note no significant variation in Rh with
increasing temperature, which might be due to an increase in the
aggregation number and a decrease in micellar solvation. Previ-
ously, Borse and co-workers found that the hydration of micelles
(hE) decreases in cationic Gemini surfactants with increasing tem-
perature [66]. By assuming that there is no substantial change in
micellar solvation, the aggregation numbers can be calculated at
various temperatures. The values in table 2 demonstrate that the
Nagg values of 14–4–14 remain predominantly constant with the
increase in temperature. A small variation in Nagg values of 14–
4–14 are in line with the similar variation in the CMC values of this
surfactant. Consistent with the present work, the previous studies
have noted a small variation of Nagg with the increase in the tem-
perature for cationic Gemini surfactants [18,21].
The values of the intermicellar interaction coefficient (kd) were
calculated from the slopes of plots of Dm versus the surfactant con-
centration (see figure SM4), as described by linear interaction the-
ory [60]. In table 2, it can be seen that the kd values are influenced
by increases in the lengths of the tail and the spacer. The intermi-
cellar interaction parameter decreases with increases in the chain
lengths of the Gemini surfactants. This behavior is mainly due to
the growth of micelles and decreases in the micellar surface charge
density [18,66]. On the other hand, an unexpected increase in kd
was found for decreasing spacer length. This increase is due to
the change from sphere to rod micellar morphology. Small angle
neutron scattering and cryo-TEM studies of the m–s–m Gemini sur-
factants revealed the formation of less curved aggregates when the
spacer is short enough [21]. Cryo-TEM showed that the 12–2–12
micelles are threadlike, whereas those of 12–4–12 are spheroidal
[13,21].
In order to examine the effects of varying the temperature on
intermicellar interactions, voltammetric experiments were carried
out for 14–4–14 over the temperature range 298 K to 318 K. Figure
3 shows the variation of Dm with temperature at three concentra-
tions. As expected, the Dm values increase with increasing temper-
ature. The kd values were obtained with linear interaction theory
and are plotted as a function of temperature in figure 4. It is obvi-
ous that kd decreases linearly with increasing temperature. Two
factors control the value of kd in colloidal systems: inter-particle
attractive or repulsive interactions. According to our results,
decreasing kd with temperature suggests a decrease in repulsive
interactions due to a reduction in surface charge density and an in-
crease attractive interactions. This temperature effect is consistent
with the results of a previous study by Borse et al. [66]. They re-
ported that the equilibrium distances (d) between the head groups
of surfactant 12–4–12 are 0.742 and 0.771 nm at T = 303 K and
323 K, respectively. An increase in the attractive interaction or de-
crease in repulsive interaction leads to micellar growth. The small
magnitude of the increase in the micellar size or Nagg (table 2) sug-
gests that the increase in attractive interaction or decrease in
repulsive interaction has only a small effect on micelle size, but
in our work the structure of Gemini surfactant is the dominant fac-
tor for determination of the micelle size. While, the results of
Charlton et al. showed a decrease in interaction parameter with
temperature due to increase in attractive interaction, then the in-
crease in the attractive interaction leads to micellar growth for Tri-
tonX-100 [56]. Further, the intermicellar interaction parameters
for the monomeric form of these surfactants such as cetyltrimeth-
ylammonium bromide (CTAB) [67], cetyltrimethylammonium
chloride (CTACl) [68] and sodium dodecyl benzene sulfonate
(SDBS) [69] increase with increasing temperature.
To examine further the observed behavior, the intermicellar
interaction energy (Coulombic potential) for two identical spheri-
cal macro-ions of diameter r was calculated [70]. A plot of U(r) ver-
sus kd is shown in figure 5. It is evident that the intermicellar
interaction parameter is a function of the Coulombic interaction
114 M. Hajy Alimohammadi et al. / J. Chem. Thermodynamics 44 (2012) 107–115
potential. The interaction parameter decreases gradually with
increases in temperature as the Coulombic interaction (U(r)/kT)
varies between 1.74 and 1.13.
4. Conclusion
In our surface tension and conductometry study of
CmH2m+1N(CH3)2(CH2)S (CH3)2 N CmH2m+1,2Br with m = 12, 14
and s = 2, 4 over the temperature range 298 K to 323 K, the varia-
tions of CMC and a with temperature have been obtained. The
CMC values pass through a minimum as the temperature is in-
creased from 298 K to 323 K. The a values increase slightly with
temperature. This study also enabled us to obtain the thermody-
namic parameters of micellization. The Gibbs free energy of micel-
lization has a weak dependence on temperature for these Gemini
surfactants. A clear linear relation (enthalpy–entropy compensa-
tion relation) was found between DH0m and DS0m for these Gemini
surfactants.
By performing CV measurements, several important micellar
parameters were estimated and the intermicellar interactions were
analyzed. The effects of varying the temperature can be interpreted
in terms of decreasing electrostatic repulsions of head groups and
increasing attractive interactions of spacers. This study has shown
that CV is a simple and sensitive technique for probing the struc-
tural changes of micelles and in particular their dependence on
the spacer and chain lengths of the hydrophobic tails of Gemini
surfactants, and for obtaining information about intermicellar
interactions in aqueous solutions.
5. Calculations
As can be seen from figure SM2, plots of solution conductivity
versus surfactant concentration are composed of two straight lines
intersecting at the CMC. We employed the method of Frahm and
that of Evans to calculate the a value.
The method of Frahm is given by [35]
a ¼ s2 =s1 ;
where s1 and s2 are the slopes k plots below and above the CMC,
respectively.
The method of Evans for calculating a is given by [36]:
1000s2 ¼ ða2 =N2=3
agg Þð1000s1  KBr Þ þ aKBr ;
 
where s1, s2 are those defined above; the KBr is the equivalent con-
ductivity of Br at infinite dilution.
The surface excess (Cmax) and the minimum area per molecule
(Amin) were calculated by using the Gibbs adsorption equation
[38,39],
Cmax =mol  m2 ¼ ð1=2:303RTÞ½dc=d log CT;P
and
1 1018
Amin =nm2  molecule ¼ ;
NA Cmax
where dc/d log C is the maximum slope in each case. The R, T, C,
and N are the gas constant, absolute temperature, concentration,
and Avogadro’s constant, respectively. The slope of the tangent at
a given concentration of the c versus log C plot was used to calcu-
late C by using curve fitting to a polynomial equation of the form
y = ax2 + bx + c.By applying the Gibbs–Helmholtz equation to
equation (2), the enthalpy of micellization can be obtained from
[18]:
1
DHmic =ðkJ  mol Þ ¼ RT 2 ð1:5  aÞð@ ln X CMC =@TÞp þ
RT 2 LnX CMC ð@ a=@TÞ: ð11Þ
To evaluate the enthalpy of micelle formation, the CMC and a values
were first correlated by using a polynomial equation [18]:
3
‘nX CMC ðTÞ ¼ a þ bT þ CT 2 þ dT ; ð12Þ
a ¼ a0 þ b0 T þ c0 T 2 ; ð13Þ
where constants a, b, c, d, a’, b’, and c’ were determined by using
least-squares regression analysis.
The enthalpy of micelle formation was then calculated numer-
ically by substituting equations (13) and (14) into equation
(12).The entropy contribution to the micellization process can be
estimated from the calculated enthalpy and Gibbs free energy val-
ues as
T DSmic ¼ DHmic  DGmic : ð14Þ
The micellar hydrodynamic radius was calculated by using the
Stokes–Einstein equation [62–65]:
kT
Rh ¼ ; ð15Þ
6pgD0m
where k is the Boltzmann constant, T is the absolute temperature,
and g is the viscosity of the solution, which can be approximated
as that of water.
The aggregation number can be computed with the following
equation:
ð4=3ÞpR3h
Nagg ¼ ; ð16Þ
½V A þ nh;A V H2 O þ bðV con þ nh;con V H2 O Þ
where VA, Vcon, and V H2 O are the molecular volumes of the Gemini
surfactants, the counter ion, and H2O, and nh,A and nh,con are the
hydration numbers of the head groups of the surfactants and coun-
ter ions [71]. Finally, b is defined as the degree of attachment.The
intermicellar interaction energy (Coulombic potential) for two iden-
ð7Þ tical spherical macro-ions of diameter r was calculated [70]
UðrÞ ¼ pee0 r2 w20 exp½jðr  rÞ=r; ð17Þ
where r is the micellar center-to-center distance, e is the dielectric
constant of the medium (H2O), e0 is the permittivity of free space, k
is the Debye–Huckle inverse screening length as determined from
ð8Þ the ionic strength of the solution, and r ¼ 2R0h , where R0h is the
micellar hydrodynamic radius. R0h can be obtained from D0m , which
can be determined with the Stokes–Einstein relation (equation
(16)). The value for r can be calculated from the micellar volume
fraction (u) (obtained from R0h ) as follows:
r ¼ 2R0h þ l; ð18Þ
ð9Þ 3
l ¼ ½8p=21=3 uðR0h Þ: ð19Þ
Appendix A. Supplementary material
ð10Þ
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jct.2011.08.007.
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JCT-11-213