J Surfact Deterg (2013) 16:77–84
DOI 10.1007/s11743-012-1393-5
REVIEW ARTICLE
Physico-Chemical Investigations of Mixed Micelles of Cationic
Gemini and Conventional Surfactants: a Conductometric Study
Naved Azum • Malik Abdul Rub • Abdullah M. Asiri •
Aftab Aslam Parwaz Khan • Anish Khan
Received: 5 February 2012 / Accepted: 17 July 2012 / Published online: 24 August 2012
Ó AOCS 2012
Abstract The interaction of cationic gemini and cationic
conventional surfactants by conductivity was systematically
overviewed, paying attention to synergism observed in mic-
ellization. These mixed systems were found to show
remarkable synergism in micelle formation. The experimental
critical micelle concentration values being lower than the
value predicted by ideal solution theory indicate that the
mixed micellization is due to attractive interaction between
the two components. Gemini/conventional systems form
mixed micelle due to attractive interactions (negative b val-
ues). The values of micellar mole fraction of constituent 1 (X1)
in surfactant mixtures are more than in the ideal state (Xideal
1 ),
which means that, the mixed micelles are rich in conventional
surfactants in comparison to that in the ideal state.
Keywords Mixed surfactant systems  Conventional
surfactants  Gemini surfactants  Interaction parameters 
Synergism  Regular solution theory
Introduction
The gemini surfactants [1, 2] (also known as dimeric surfac-
tants [3, 4]), have generated interest in colloid chemistry due to
N. Azum (&)  M. A. Rub  A. M. Asiri 
A. A. P. Khan  A. Khan
Center of Excellence for Advanced Materials Research,
King Abdulaziz University, P.O. Box 80203, Jeddah 21589,
Saudi Arabia
e-mail: navedazum@gmail.com
N. Azum  M. A. Rub  A. M. Asiri  A. A. P. Khan  A. Khan
Chemistry Department, Faculty of Science,
King Abdulaziz University, P.O. Box 80203,
Jeddah 21589, Saudi Arabia
their superior performance over conventional surfactants in
various applications. Menger et al. [5–7] assigned the term
‘‘gemini’’ to the bis-surfactants having a rigid spacer such as
benzene or stilbene. The term was then extended to other bis or
double tailed surfactants, irrespective of the nature of the
spacer. Geminis are considerably more surface active than
conventional monomeric surfactants. All geminis possess at
least two hydrophobic chains with two ionic or polar head
groups having different spacers [8], such as short or long
flexible chains of methylene groups, rigid (stilbene), polar
(polyether) and non-polar (aliphatic, aromatic) groups (Fig. 1).
The head group can be positive (ammonium) or negative
(phosphate, sulfate, carboxylate) whereas the polar nonionics
may be polyether or sugar-based. The majority of geminis have
a symmetrical structure with two identical head groups and two
identical chains. Some unsymmetrical geminis with three or
more polar groups or tails have recently been reported [9–15].
In contrast to the conventional surfactants (single head/
single tail), the gemini surfactants with their unique
chemical structures have been found to possess properties
which are superior to those of the former. These include
low critical micelle concentration (CMC) values and
unusually high surface activity, better solubilization and
multiplicity of aggregation [2], as a result of which many
manufacturers and researchers have evinced keen interest
in gemini surfactants. Noteworthy among these gemini
surfactants, the cationic alkanediyl-a,x-bis(alkyldimethy-
lammonium bromide) type, designated m-s-m, where m
refers to the length of the alkyl tails and s is the number of
methylene units that make up the alkyl spacer, has received
more attention. The three structural elements—hydrophilic
head group, a hydrophobic tail, and their linkage—may be
varied to change the properties of the gemini surfactants.
Most of the practical surfactant applications rely on
mixtures of surfactant/surfactant [16, 17] or surfactant/
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Spacer Head
[50] observed that in gemini–zwitterionic systems aggre-
Tail Head Tail
gation number decreases with increase in the mole fraction
of gemini whereas with the number of carbon atoms in the
tail of the gemini surfactant the curve passes through a
maximum. However, mixed micellization of gemini sur-
factants with conventional ones has not received full
Fig. 1 Schematic representation of a gemini surfactant
attention that it deserves.
In this overview paper, we have reviewed the potential
polymer [18], either because commercial surfactants are use of mixed micellization of cationic gemini surfactants
always mixtures due to raw materials used and method of with cationic conventional surfactants broadly, which will
manufacture or their improved action over single pure facilitate a reader to study a particular research at a glance.
surfactants [16, 19]. For example, liquid detergents usually
contain synthetic anionic surfactants, nonionic surfactants
and natural soaps [20]. When two (or more) types of sur- Results and Discussion
factants are in solution, a complex balance of intermolec-
ular forces is responsible for the formation of mixed Critical Micelle Concentration (CMC)
micelles against the formation of micelles by one type
of surfactant. Binary mixtures formed by different surfac- Solutions Containing Single Surfactants
tants such as nonionic/nonionic [21–25], anionic/nonionic
[26–30], cationic/nonionic [31–33], cationic/cationic [34– Aqueous solutions of the conventional and gemini binary
36], cationic/anionic [37, 38] and anionic/anionic [39–41], systems have been characterized through conductivity
have been studied in recent years by using a variety of measurements [51–59]. It seemed one of the most
techniques, i.e., surface tension, conductivity, fluorescence, straightforward techniques used due to high sensitivity and
small-angle neutron scattering (SANS), nuclear magnetic reproducibility. Differential conductivity (dj/dc) plots
resonance (NMR), light scattering, etc. Micelles consti- were also used [54, 55], to check the CMC. A comparison
tuted of nonionic surfactants show ideality while that of of such plots with that of conventional has some advanta-
ionic surfactants exhibit nonideal behavior resulting from ges, particularly when the break point in the j versus c is
synergistic (attractive) or antagonistic (repulsive) interac- not sharp. A derivative curve shows an instantaneous
tions [42–45]. It may also be observed that similarly decrease in CMC region and hence, the center of the
charged surfactants of different molecular structure may reversed sigmoid curve gives the value of CMC (a repre-
exhibit both ideal [34, 36] and non-ideal [26] behaviors. sentative plot shown in Fig. 2). In aqueous medium, the
However, there is lack of data regarding the effect of ionic surfactant solutions of low concentration behave as simple
head as it is expected to be less than that of chain length electrolyte solutions and most of the surfactant molecules
[46]. Since interactions between ionic surfactants are exist as free monomers. However, above a certain
generally governed by the electrostatic forces between their
head groups [47], it would be expected that such interac-
tion would be stronger for surfactants having two ionic
groups. Binary mixtures of gemini surfactants with single
tail surfactants have greater probability of exhibiting syn-
ergism although the degree of synergism is governed by the
head group variations and also by chain length variations.
Owing to the various applications and difference in prop-
erties of mixed systems and individual components, a study
of mixed systems of gemini and conventional surfactants
should be very important for both practical and funda-
mental aspects as their properties will be dictated by their
aggregation behavior and composition. Zana et al. [48]
found that aggregation number of mixed systems of cat-
ionic gemini and nonionic surfactant goes through a min-
imum with increase in gemini concentration. De et al. [49]
found that with the increase in cetyltrimethylammonium
Fig. 2 Plots of specific conductivity (j) and first derivative of
bromide (CTAB) concentration, the mixed CTAB ? gemini specific conductivity (dj/dc) of 14-4-14 ? TTAB versus total
systems undergo sphere to rod transition. Bakshi and Singh surfactant concentration [c] at aTTAB 0.2

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concentration, known as critical micelle concentration,
micelles formation takes place. In a homologous series, the
CMC normally decreases logarithmically with the number
of carbon atoms (nc) in the chain according to the typical
relation log (CMC) = A - B  nc where A and B are con-
stants, specific to a homologous series under constant con-
ditions of temperature and pressure.
The major driving force for micelle formation is the
hydrophobic interaction. Entropy increases when water
molecules around the hydrophobic parts of the surfactants
tails are released in the process of micellization. As the
length of hydrophobic part increases more water molecules
are released resulting in more increase in entropy; hence
micellization takes place at lower amphiphile concentration
(i.e., lower CMC). Increase in the length by –CH2– group,
decreases CMC by 50 %. It is well known [60, 61] that
increase in length of surfactant’s tail by –CH2– affects
other micellar properties, e.g., the dissociation degree
decreases nearly 25 %. However, change in carbon atom
number in head group has little effect on micellar proper-
ties. Junquera and Aicart [62] observed that when a methyl
group of dodecyltrimethylammonium bromide head group
is replaced by an ethyl group the CMC decreased by 8 %
only while dissociation degree increased by about 8 %.
Azum et al. [51, 52, 54, 55] also show similar behavior.
The CMC of CTAB is 75 % lower than that of TTAB
whereas that of CPB is 35 % lower than that of CTAB.
However, the change in counterion from Br̄ (in CPB) to Cl̄
(in CPC) affects the CMC value slightly. Presence of two
alkyl chains in m-s-m gemini surfactants makes the mol-
ecule more hydrophobic. The greater the hydrophobicity of
the molecule, the greater the distortion of the water struc-
ture and the greater the tendency to form micelles. Hence
the CMC of 14-s-14 is about 86 % less than that of CTAB
and 96 % from that of TTAB. In case of gemini surfac-
tants, two hydrophobic chains break the water structure and
thus increase the tendency to form micelles more in com-
parison to single chain surfactants, hence CMC values are
lower for gemini surfactants.
Solutions Containing Surfactant Mixtures
An aqueous solution containing surfactant mixtures also
forms aggregates, but the tendency of aggregation can be
different from that of the pure surfactants. The mixed
micelle formation between the unlike components of sur-
factants can be evaluated by using the following equation
1 Xn
ai
¼ ð1Þ
CMC i¼1
CMC i fi
where ai is the stoichiometric mole fraction in the mixture
and CMC* is the ideal CMC value of the mixture and fi is its
79
activity coefficient. For the ideal systems, fi = 1, and the
above equation reduces to Clint equation or model [23, 63],
based upon pseudophase thermodynamic formulation. The
phase separation model is a very important and useful tool to
describe micelle formation. In this model, the surfactant
monomers in bulk phase, the micelles, and the monomers at
the interface are supposed to be in equilibrium. The micelles
are treated as a separate phase and the condition of equality of
the chemical potential of different phases is applied. Clint’s
equation can be used to relate the CMC values as
Xn
1 ai
 ¼ ð2Þ
CMC CMC i
i¼1
For two surfactants 1 and 2 with CMC values CMC1 and
CMC2,
1 a1 a2
 ¼ þ ð3Þ
CMC CMC1 CMC2
This is an idealization which neglects the interaction
among different surfactants in the aggregated state and
considers the CMCs of the individual components reflecting
their relative tendency toward micellization in the mixed
state. The theory is, therefore, an oversimplification and can
be applied only in fairly dilute solutions (systems with very
low CMCs). The theory is, however, a tool, divergence from
which in the positive and negative side signifies antagonistic
and synergistic behavior, respectively. At first let us describe
the synergistic effect of the mixed systems of gemini (14-s-
14 and 16-s-16, where s = 4, 5, 6) with conventional
surfactants (CTAB, TTAB, CPB and CPC) in term of CMC
and CMC*. One can see from the Fig. 3 that the CMC values
are always smaller than the CMC* values and the difference
between the two increases with the increase in mole fraction
of the conventional surfactant. Tikariha et al. [56] have
reported similar observation for the interaction of gemini
(16-10-16) with conventional surfactants. A lower CMC
value than the corresponding CMC* value indicates that
mixed micellization is due to attractive interactions between
the two components of the mixtures (synergism). The
intercalation of two hydrophobic tails of gemini into the
conventional (CTAB, TTAB, CPB and CPC) surfactants
micelles improves hydrophobic environment in the mixed
state in comparison to that in pure state as were reported
previously [57–59].
Molecular Interactions in Mixed Systems
In order to investigate the nature of interactions among the
components, various other parameters can be calculated,
using Rubingh’s model [64].
Rubingh model [64] is the first model developed for
nonideal mixed systems. It is based on regular solution
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0.55
0.75
14-4-14
0.50 14-4-14 0.70
14-5-14
14-5-14 0.65
0.45 14-6-14
14-6-14 0.60
CMC, CMC*/ mM

CMC, CMC*/ mM
0.40 0.55
0.50
0.35
0.45
0.30 0.40
0.35
0.25
0.30
0.20 0.25
0.20
0.15
0.15
0.10 0.10
0.0 0.2 0.4 0.6 0.8 0.0 0.2 0.4 0.6 0.8
αCTAB αTTAB

0.44 0.40
0.42 14-4-14 14-4-14
0.40 14-5-14 14-5-14
0.35
0.38 14-6-14 14-6-14
0.36
CMC, CMC*/ mM

CMC, CMC*/ mM
0.34 0.30
0.32
0.30
0.28 0.25
0.26
0.24 0.20
0.22
0.20
0.18 0.15
0.16
0.14
0.10
0.0 0.2 0.4 0.6 0.8 0.0 0.2 0.4 0.6 0.8
αCPB αCPC

Fig. 3 Critical micelle concentrations for binary mixtures of 14-s-14 ? conventional. Solid lines represent experimental data (CMC) and dashed
lines were calculated from Clint’s model (CMC*)

approach for the treatment of a nonideal mixing, and due to determined from experimental values of CMC using the
its simplicity, it has been mostly used, even after devel- following equations
opment of more complex models. The nonideality is
introduced with the inclusion of the activity coefficients, fi, b ¼ ½lnðCMCa1 =CMC1 X1 Þ=ð1  X1 Þ2 ð7Þ
on Eq. (2), i.e.,
½X12 lnðCMCa1 =CMC1 X1 Þ
X n ¼1 ð8Þ
1 ai 2
ð1  X1 Þ ln½CMCð1  a1 Þ=CMC2 ð1  X1 Þ
 ¼ ð4Þ
CMC f CMCi
i¼1 i
where X1 is the micelle mole fraction of surfactant 1 (i.e.,
where, in case of a binary solution, conventional) in the mixed micelles. Equation (8) was
solved iteratively to obtain the values of X1. The micelle
f1 ¼ exp½bð1  X1 Þ2  ð5Þ mole fraction in the ideal state (Xideal ) was also evaluated
1
and by applying Motomura’s theory [66], which is based upon
  excess thermodynamic quantities, as
f2 ¼ exp bX12 ð6Þ
X1ideal ¼ ½ða1 CMC2 Þ=ða1 CMC2 þ ð1  a1 ÞCMC1 Þ ð9Þ
The b parameter can be interpreted in terms of an
energetic parameter that represents the Gibbs excess free It is clear from the data (Table 1) that in most of the
energy of mixing, which, according to the regular solution cases the average X1 values are always more than Xideal
1 ,
approximation, is true only in the case when the excess which means that, even in a low conventional surfactant
entropy of mixing is zero [64, 65]. b parameter can be region (i.e., with low a1 values), the mixed micelles are

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Table 1 Various average

System Average values
physicochemical parameters for
m-s-m ? conventional mixed X1 Xideal
1 –b f1 f2 –DGex (J mol-1)
systems at 303 K, evaluated on
the basis of conductivity 14-4-14 ? CTAB 0.205 0.173 0.815 0.597 0.966 0335
measurements [51–54] 14-5-14 ? CTAB 0.266 0.185 1.417 0.466 0.905 0697
14-6-14 ? CTAB 0.272 0.190 1.481 0.456 0.896 0739
14-4-14 ? TTAB 0.132 0.054 1.575 0.305 0.973 0455
14-5-14 ? TTAB 0.172 0.058 2.278 0.210 0.935 0817
14-6-14 ? TTAB 0.206 0.060 3.089 0.143 0.877 1273
14-4-14 ? CPB 0.259 0.232 0.532 0.766 0.941 0252
14-5-14 ? CPB 0.314 0.241 1.280 0.542 0.882 0622
14-6-14 ? CPB 0.332 0.251 1.600 0.492 0.834 0818
14-4-14 ? CPC 0.279 0.260 0.264 0.848 0.985 0097
14-5-14 ? CPC 0.306 0.271 0.607 0.727 0.950 0260
14-6-14 ? CPC 0.346 0.281 1.149 0.599 0.891 0566
16-4-16 ? CTAB 0.096 0.039 1.217 0.411 0.967 0336
16-5-16 ? CTAB 0.177 0.088 1.530 0.424 0.933 0582
16-6-16 ? CTAB 0.244 0.06 4.088 0.106 0.748 1898
16-4-16 ? TTAB 0.162 0.0665 4.946 0.035 0.864 1660
16-5-16 ? TTAB 0.143 0.019 3.486 0.126 0.901 1125
16-6-16 ? TTAB 0.218 0.016 6.089 0.027 0.714 2647
16-4-16 ? CPB 0.120 0.058 1.418 0.545 1.198 0414
16-5-16 ? CPB 0.226 0.124 1.732 0.379 0.927 0698
16-6-16 ? CPB 0.212 0.0867 2.374 0.248 0.885 0953
16-4-16 ? CPC 0.134 0.068 1.415 0.404 0.958 0537
16-5-16 ? CPC 0.239 0.129 1.772 0.381 0.879 0836
16-6-16 ? CPC 0.189 0.101 1.601 0.372 0.909 0637

rich in conventional surfactants in comparison to that in
ideal mixing state (i.e., Xideal
1 ). Tikariha et al. [56] have
reported similar observation. Banipal et al. [57] have
reported a reverse effect. Further, as the length of spacer
increases from 4 to 6, the value of X1 becomes larger and
the difference between X1 and Xideal1 values increases. This
means that at the same mixture composition, as the spacer
chain length changes from 4 to 6, the contribution of
gemini surfactant decreases and gemini molecules
contribute less as compared to their ideal state. Zana
et al. [67] observed that the CMC values show a peaked
behavior with the spacer length having a maximum at
s = 5 or 6. This is the equilibrium distance between the
two head groups and surfactants with spacer length of less
than 5 or 6 micellize easily while spacer of 5 or 6 carbon
atoms prefers to lie in stretched rather than in the curved
form. Therefore, at the same mixture composition, as the
spacer chain length changes from 4 to 6 the contribution of
gemini molecules is less in mixed micelles as compared to
their ideal state.
The b values demonstrate the extent of interaction
between the two surfactants which leads to the deviation
from ideality. Negative b values mean attractive interac-
tions between the two components in a mixed micelle more
than the self-attraction of the two surfactants before mix-
ing. A zero value indicates ideal mixing while positive
values show less attraction after mixing (antagonism).
It can be seen from the data (Table 1), the average
values of interaction parameter, bav, come out to be neg-
ative, indicate attractive interaction among the gemini and
conventional surfactants in mixed micelles. It is clear from
the data that the magnitude of bav is maximum with TTAB.
According to Rodriguez et al. [68], binary systems where
components have a tendency to form micelles of different
shapes, i.e., different packing parameters, lead to nonideal
behavior. Speaking generally, the binary systems whose
components have a tendency to form micelles of similar
shapes are expected to be more ideal than those with a
tendency to form micelles of different shapes. Apart from
this, increase in spacer length also affects synergistic
interactions, most likely due to the increase in hydropho-
bicity at the level of head group of amphiphiles in the
micellar phase. Rodriguez et al. [53] have reported the non-
ideality of the DTAB ? 12-s-12 binary systems, increases
when s decreases from 3 to 4, and for the s = 4, 5 the non-
ideality is similar. For CTAB ? 16-s-16 systems the non-
ideality increases from s = 2 to 4, although s = 4–6 have
the same magnitude of non-ideality. In the comparison of

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CPB and CPC mixed system with gemini surfactant, the
least negative value of bav with CPC is due to the steric
hindrance of bulky pyridinium head group of CPC. Banipal
et al. [57] have reported similar observations for the
interaction of gemini surfactant (14-2-14) with some con-
ventional surfactants.
The values of activity coefficients, f1 and f2, can be
calculated from Eqs. (5) and (6). If the values are found to
be less than unity nonideal behavior of the mixed systems,
was confirmed.
The activity coefficients were used to calculate excess
free energy of mixing by the relation
DGex ¼ RT½X1 ln f1 þ ð1  X1 Þ ln f2  ð10Þ
The average negative DGex values [51, 52, 54, 55], thus
obtained (Table 1) suggest that the mixed micelles are
more stable than the micelles of individual components.
High DGex values (average) of 14-s-14 ? TTAB fall in
line with b values and are self explanatory in the light of
above discussion of b.
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Author Biographies
Naved Azum is an assistant professor at the Center of Excellence for
Advanced Materials Research at King Abdulaziz University, Jeddah,
Saudi Arabia. He received his Ph.D. degree from Aligarh Muslim
University, India. His research interest is the physicochemical
behavior of micellar solutions (gemini as well as conventional).
Malik Abdul Rub received his M.Sc. and Ph.D. degrees from
Aligarh Muslim University. He is currently an assistant professor of
the Center of Excellence for Advanced Materials Research, King
Abdulaziz University. His current research interests are mixed
micellization study of amphiphilic drugs with different additives,
and clouding phenomenon in amphiphilic systems.
Abdullah Mohammed Ahmed Asiri is currently a professor and the
chairman of the chemistry department of the Faculty of Science at
King Abdul Aziz University. He completed his Ph.D. at the
University of Wales, College of Cardiff, UK. He is the director of
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the Center of Excellence for Advanced Materials and Research. His
current research interests are smart molecules and materials, novel
photochromic and thermochromic systems, organic synthesis of
heterocyclic compounds, synthesis of polymers functionalized with
organic dyes and nano hybrid materials.
Aftab Aslam Parwaz Khan was awarded his Ph.D. degree from
Aligarh Muslim University. He is currently an assistant professor at
the Center of Excellence for Advanced Materials Research, King
123
J Surfact Deterg (2013) 16:77–84
Abdulaziz University. His current interest in research is reaction
mechanisms and medicinal chemistry.
Anish Khan completed his Ph.D. at Aligarh Muslim University, and
his post-doc at the University of Science in Malaysia. Currently he is
an assistant professor at the Center of Excellence for Advanced
Materials Research, King Abdulaziz University. His current research
interest is synthesis of nano hybrid materials and their application for
biosensors for neurotransmitters and chemical sensors.