Journal of Colloid and Interface Science 385 (2012) 96–110

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Journal of Colloid and Interface Science

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Interfacial composition, thermodynamic properties, and structural parameters

of water-in-oil microemulsions stabilized by 1-pentanol and mixed surfactants
Kaushik Kundu, Gourhari Guin, Bidyut K. Paul ⇑
Surface and Colloid Science Laboratory, Geological Studies Unit, Indian Statistical Institute, 203, B.T. Road, Kolkata 700 108, India

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

Article history: The present study is focused on the evaluation of the interfacial composition, thermodynamic properties,
Received 9 April 2012 and structural parameters of water-in-oil mixed surfactant microemulsions [(cetylpyridinium chloride,
Accepted 20 June 2012 CPC + polyoxyethylene (20) cetyl ether, Brij-58 or polyoxyethylene (20) stearyl ether, Brij-78)/
Available online 29 June 2012
1-pentanol/n-heptane, or n-decane] under various physicochemical environments by the Schulman
method of cosurfactant titration of the oil/water interface. The estimation of the number of moles of 1-pent-
Keywords: anol at the interface ðnia Þ and bulk oil ðnoa Þ and its distribution between these two domains at the threshold
The dilution method
level of stability have been emphasized. The thermodynamics of transfer of 1-pentanol from the continuous
Mixed surfactant microemulsion
Interfacial composition
oil phase to the interface have been evaluated. nia ; nia , standard Gibbs free energy ðDG0t Þ, standard enthalpy
Thermodynamic properties ðDH0t Þ, and standard entropy ðDG0t Þ of transfer process have been found to be dependent on the molar ratio of
Structural parameters water to surfactant (x), type of nonionic surfactant and its content (XBrij-58 or Brij-78), oil and temperature. A
correlation between ðDH0t Þ and ðDS0t Þ is examined at different experimental temperatures. Bulk surfactant
composition dependent temperature insensitive microemulsions have been reported. Associated structural
parameters, such as droplet dimensions and aggregation number of surfactant and cosurfactant at the drop-
let interface have been evaluated using a mathematical model after suitable modifications for mixed surfac-
tant systems. In light of these parameters, the prospect of using these microemulsion systems for the
synthesis of nanoparticles and the modulation of enzyme activity has been discussed. Correlations of the
results in terms of the evaluated physicochemical parameters have been attempted.
Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction alcohol content, imparts an additional advantage to modulate size

Water-in-oil microemulsions (w/o) or reverse micelles (RMs)
are inverted micelles that spontaneously organize from a mixture
of water, surfactant (and/or short chain lipophilic alcohol as cosur-
factant) and nonpolar solvent, allowing encapsulation of small
water pools in a low viscosity, nonpolar solvent under stable condi-
tions (temperature, pressure, and composition) [1,2]. The proper-
ties of confined water differ considerably from those of the bulk
water due to geometrical constraints of the environment and
molecular interactions at the oil/water interface [3,4]. Surfactants,
due to their diphilic nature, get adsorbed at the oil/water interface
to render stability to the dispersion by preventing coalescence.
However, the addition of alcohol (cosurfactant) effectively changes
the originally unfavorable packing geometry of the surfactant mol-
ecules, which in turn, adjusts the spontaneous curvature of the film
to a negative value (curvature toward aqueous domain), and pro-
duces a stable surfactant/alcohol mixed interfacial film. Further,
cosurfactants partition themselves among the oil, water, and the
interface domains depending upon the lipophilicity. By changing
⇑ Corresponding author.
E-mail addresses: bidyut@isical.ac.in, bidyut.isical@gmail.com (B.K. Paul).
of the water pools and surface dynamics. Therefore, without a
quantitative description of the dependence of the partition equlib-
ria on the system composition under varied physicochemical envi-
ronments, a full understanding of quaternary microemulsions
cannot be attained.
Recently, it has been reported that the addition of nonionic sur-
factant into the ionic surfactant modifies the interface and produces
considerable change in the elastic rigidity of the interface, which in
turn affects the water solubilization capacity and water structure
inside w/o microemulsions depending upon the extent of penetra-
tion of the nonionic surfactant in the interface and the water pool,
which can be measured using different techniques [5–12]. How-
ever, most of these studies are concerned with AOT [sodium
bis(2-ethylhexyl) sulfosuccinate or Aerosol OT] as a basic amphi-
phile, with some exceptions like cationic or anionic or their blends
with nonionic [9–11], as AOT forms easily water-in-oil microemul-
sions in apolar solvent containing a small amount of water. In the
matter of understanding of the nature of the oil/water interface,
microstructure and water pool of mixed surfactant w/o microemul-
sions involving ionic surfactants of different charge types and head
groups (viz., alkyltrimethylammonium salts or alkylpyridinium
salts or sodium dodecylsulfate) and nonionic surfactants (polyoxy-

0021-9797/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.06.057
 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
ethylene ether surfactants) and alcohol is not much reported. As re-
ports on the use of the hydrophilic surfactant (cationic or anionic or
nonionic) in combination with alkanol (cosurfactant) as templates
for shape and size controlled synthesis of nanoparticles of noble
metals and bimetallic nanoparticles [13–15], packaging design of
nanomaterials [16], sustained-release drug molecules [17] and en-
zyme activity [18,19], we contemplate to propose microemulsions
comprising the blends of cationic or anionic surfactant with non-
ionic surfactant(s), as model systems for such studies. Hence, to
understand chemical reactivity of a single or mixed species either
inside the water pool or at the interface of a quaternary w/o micro-
emulsion, the detailed knowledge on (i) interfacial composition
such as relative population of surfactant(s) and cosurfactant at
the oil/water interface, (ii) the distribution of cosurfactant between
the interface and bulk oil phase vis-à-vis the thermodynamics of
this transfer process of cosurfactant, (iii) the number and the size
of the droplets, and (iv) physicochemical characteristics of the en-
trapped water. These parameters are strongly influenced by the
type and alkyl chain length of oil and the amphiphiles (surfactant
or cosurfactant) [20]. All these parameters, (except (iv) which can
be determined using fourier transform infrared spectroscopy, FTIR,
and compressibility measurements [21]), can be evaluated (with-
out using sophisticated instruments) from the dilution method
(the Schulman method of cosurfactant titration of the oil/water
interface) [22]. This simple but elegant method is accomplished
by adding oil at a constant water and surfactant level to destabilize
an otherwise stable w/o microemulsion and then restabilizing it by
adding a requisite amount of cosurfactant (alcohol) with constant
composition of interface and continuous phase. For these reasons,
the dilution method has been widely used by a number of workers
to estimate the parameters involved in the transfer of alcohol from
the bulk oil to the interface [23–40]. Though Gu et al. [41], criticized
the method on the basis of energetic and distribution parameters
from calorimetric data, it has been confirmed to be correct by Mou-
lik et al. [42] and Palazzo et al. [28] later on. Palazzo et al. [28] fur-
ther pointed out that the method has applications in scattering and
diffusion studies, because it provides extrapolation to single-parti-
cle properties by reducing inter-particle interactions of the micro-
emulsion system without changing its composition.
Physicochemical studies involving mixed surfactant water-in-
oil (w/o) microemulsions (including ionic liquid as cationic surfac-
tant) by the dilution method are rarely reported [38–40]. Keeping
in view of the importance of microemulsion properties obtained
from our previous reports [32,38], the present work is emphasized
on the evaluation of the interfacial composition, thermodynamics,
and structural parameters as a function of mixing ratio of cationic
and nonionic surfactants, x, alcohol, chain length of oil and non-
ionic surfactant, and temperature by the dilution method. The cat-
ionic and nonionic surfactants used were cetylpyridinium chloride
(CPC), polyoxythelene (20) cetyl ether (Brij-58) and polyoxythe-
lene (20) stearyl ether (Brij-78), 1-pentanol (Pn) as cosurfactant,
heptane (Hp) and decane (Dc) as oils, respectively. The aim of this
work is to assess the changing behavior of the interface arising out
of the addition of Brij-58 and Brij-78 (both with POE chain (20) as
polar head group, but differ in hydrocarbon chains, i.e., C16 and C18,
respectively) to CPC (with C5H5N+H head group and C16 hydrocar-
bon chain) in oils of different chain length (Hp, C7 and Dc, C10) at
different physicochemical environments. Obviously, the transfer
of Pn from bulk oil phases to the interface vis-à-vis the distribution
constant (Kd) is expected to be influenced by the molecular inter-
actions of all the constituents, leading to changed molecular
arrangement at the interface. Correlations of the results in terms
of the evaluated physicochemical parameters have been analyzed.
It is noteworthy to mention that the choice of all the ingredients in
the mixed surfactant microemulsions is not arbitrary. The cationic
surfactant, CPC is chosen due to its better solubilization capacity
97
than the corresponding quaternary ammonium salts of equal chain
length when coupled with cosurfactant, and medicinal properties,
chemical, and biophysical studies [43–45]. Due to unique proper-
ties (viz. low toxicity and irritant, biodegradability, better solubil-
ity properties in microemulsions, and more tolerance toward
electrolytes), non-ionic surfactants of different polar head groups
and hydrophobic moieties are used in various spheres [19,46–49].
It is believed that the findings are expected to improve the basic
understanding of the formation and characterization of the
interface that imparts stability to mixed surfactant w/o microemul-
sions from a physicochemical and thermodynamical point of view.
According to our knowledge, such a comprehensive study on mixed
surfactant microemulsion systems using the dilution method is not
reported earlier.
The Nomenclature and Abbreviations used in this article are
presented in Appendix A.
2. Experimental section
2.1. Materials
Cationic surfactant (cetylpyridinium chloride (CPC)) was 99%
pure product of Sigma–Aldrich, USA. Nonionic surfactants (poly-
oxyethylene (20) cetyl ether (Brij-58) and polyoxyethylene (20)
stearyl ether (Brij-78)) were obtained from Sigma, USA. The oils,
n-heptane (Hp) (>99%) and n-decane (Dc) (>99%), and the alkanol,
1-pentanol (Pn) (99.5%) were products of Merck, Germany. All
these chemicals were used without further purification. Doubly
distilled water of conductivity less than 3 lS cm1 was used in
the experiment.
2.2. Methods
The dilution experiment (the Schulman method of cosurfactant
titration) is performed as described earlier [26,27,38,42]. The pro-
cedure of this experiment at different physicochemical environ-
ments has been presented in Supplementary material (Section 1).
2.3. Theoretical backgrounds
2.3.1. Basics of the dilution method and evaluation of thermodynamic
parameters
For a quaternary water-in-oil microemulsion system composed
of water/surfactant/alkanol (cosurfactant)/oil, the solubilization of
water is governed by the distribution of alkanol molecules be-
tween oil and the interface at a fixed temperature. A small amount
of alkanol may remain solubilized in the aqueous phase depending
on its lipophilicity. A threshold amount of alkanol is required to
stabilize a water-in-oil dispersion at a fixed x. As a result, an
appropriate distribution constant (Kd) is attained and governs alk-
anol molecules distributed between the interfacial region (consist-
ing of surfactant molecules) and the oleic phase at a fixed
temperature. The stable w/o microemulsion gets disrupted when
excess oil is added and the system splits up into two distinct
phases. Again, a threshold amount of alkanol is necessary to restore
the w/o microemulsion equilibrium. This process is repeatedly fol-
lowed in the dilution experiment.
The concentrations of alkanol at the interface and in the bulk oil
phase were estimated to get Kd by the dilution experiment in light
of the physicochemical rationale elaborated by Moulik et al.
[26,42], Hait and Moulik [27], Mitra et al. [38], and Zheng et al.
[30,31]. na is given by the relation,
na ¼ nia þ nw o
a þ na ð1Þ
Since the solubility of alkanol in the oil is constant at a given
temperature, the constant ko can be written as
98 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110

noa The standard state herein considered is the hypothetical ideal

ko ¼ ð2Þ
no state of the unit mole fraction.
Combining Eqs. (1) and (2), we get
2.3.2. Evaluation of structural parameters
na ¼ nia þ nw
a þ ko no ð3Þ
This section has been dealt in Supplementary material (Section
Since the moles of alkanol in the interface and in the dispersed 2).
phase (water) depend on the surfactant concentration, Eq. (3) may
be converted into a more convenient form by dividing throughout
3. Results and discussion
by ns to give

na nia þ nw no 3.1. Interfacial composition of single and mixed surfactant based

a
¼ þ ko ð4Þ microemulsion
ns ns ns
In our experiment, negligible water solubility of Pn leads to 3.1.1. Effect of water content (x) on compositional variations ðnia =ns Þ
nw
a  0 [28]. Thus, above equation becomes, The dilution method was used for mixed surfactant microemul-
sions CPC/Brij-58 (or, Brij-78)/Hp (or, Dc)/Pn/water with varying x
na nia no
¼ þ ko ð5Þ (=10, 20, 30, 40, and 50) at a fixed composition, XBrij-58 or Brij-78 = 0.2
ns ns ns and temperature (303 K). From the data collected, graphs were
A plot of na/ns against no/ns should yield the values of the slope constructed by plotting na/ns against no/ns according to Eq. (5). Rep-
(S) and the intercept (I). Slope (S) is actually ko and noa can be deter- resentative illustration is depicted in Fig. 1. Other figures are not
mined from Eq. (2). On the other hand, nia can be calculated from exemplified here. The plots were strikingly linear. nia ; noa , Kd and
the intercept (I), which is equal to nia =ns . DG0t , as obtained from Eqs. (5)–(8), are presented in Table 1.
The partition of Pn between the continuous oil phase and the Fig. 2 represents the plot of nia =ns (compositional variation repre-
interface of the droplet can be expressed in terms of Kd. Kd can sents molar ratio of cosurfactant and surfactants at the interface)
be calculated from the ratio of mole fraction of Pn in the interfacial vs. x. It has been observed that nia or ðnia =ns Þ increases with in-
layer ðX ia Þ to the mole fraction of Pn in the bulk oil phase ðX oa Þ, crease in x up to 30 (i.e., reaches a maximum) and thereafter grad-
ually decreases up to x = 50 for all these microemulsion systems.
X ia nia =ðnia þ ns Þ nia ðnoa þ no Þ In our previous report [32], similar transition in compositional
Kd ¼ ¼ ¼ ð6Þ
X oa noa =ðnoa þ no Þ noa ðnia þ ns Þ variations ðnia =ns Þ with varying x was observed for CPC/Pn/Dc or
Dd/water systems at 303 K. Maxima were exhibited at x = 30
Dividing numerator and denominator by nia noa and putting the (Dc) and x = 20 (Dd). Further, similar transition was also reported
values of the slope (S) and the intercept (I) from Eq. (5), we get by Hait and Moulik [27] and Zheng et al. [30,31] involving cationic
ð1 þ no =noa Þ ð1 þ 1=SÞ Ið1 þ SÞ surfactant (CPC) or zwiterionic surfactants (C12-s-C122Br or C12-
Kd ¼ ¼ ¼ ð7Þ EOx-C122Br, where s = 2–6 or x = 1–3, respectively), and Bardhan
ð1 þ ns =nia Þ ð1 þ 1=IÞ Sð1 þ IÞ
et al. [50] involving blends of CTAB and C16E20. A possible explana-
tion for this type of trend can be presented in light of molecular
DG0t is obtained from the relation, interactions (viz. electrostatic interaction between ionic hydro-
philic groups, ion–dipole interaction between ionic and nonionic
X ia Ið1 þ SÞ
DG0t ¼ RT ln K d ¼ RT ln ¼ RT ln ð8Þ hydrophilic groups, and steric interaction between bulky head
X oa Sð1 þ IÞ groups) between the constituents [viz. surfactants (both cationic
and nonionic), cosurfactant] involved in the transfer process with
DH0t can be evaluated by the van’t Hoff equation. Thus, the help of a schematic representation (Scheme 1).
In this report, CPC [with (C5H5N+H) as polar head group and ce-
½@ðDG0t =TÞ=@ð1=TÞp ¼ DH0t ð9Þ tyl (C16) hydrocarbon chain] and Brij-58 or Brij-78 [with same po-
lar head group of 20 POE chains and cetyl (C16) or stearyl (C18)
Since the dependency of ðDH0t =TÞ on (1/T) are nonlinear for all
hydrocarbon chain, respectively] are in the mixed state of different
these systems (plot of ðDG0t =TÞ vs. (1/T) for CPC/Brij-78/Pn/Dc/
water system is depicted in Fig. S1 (supplementary material), same
plots for other systems have not been exemplified), a two-degree
polynomial equation of following form is used:
!    2
DG0t 1 1
¼ A þ B1 þ B2 ð10Þ
T T T

The differential form of the relation helps to evaluate DH0t . Thus,

 
@ðDG0t =TÞ 1
¼ B1 þ 2B2 ¼ DH0t ð11Þ
@ð1=TÞ T
where A, B1, and B2 are the polynomial coefficients.
Then, the Gibbs–Helmholtz equation is used to evaluate DS0t ,

DH0t  DG0t
DS0t ¼ ð12Þ
T
Fig. 1. Plot of na/ns vs. no/ns according to Eq. (5) for mixed surfactant w/o
The evaluation of ðDC 0p Þt follows from the relation,
microemulsions comprising CPC and Brij-58 (0.5 mmol) and Hp (2 ml) stabilized by
Pn with different x (=[water]/[surfactant]) at XBrij-58 = 0.2 and at constant temper-
½ðDC 0p Þt  ¼ ð@ DH0t =@TÞp ð13Þ
ature of 303 K. (The parenthetic values indicate the R2-values).
 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110 99

proportions, that is, XBrij-58 or Brij-78 = 0.2. At the threshold level of

Interfacial and bulk compositions of 1-pentanol, distribution constant and free energy of its transfer from heptane and decane to the interface for w/o microemulsion containing 2 ml oil, 0.5 mmol of surfactant at constant temperature

DG0t (kJ mol1) CPC/Brij-58/Pn/Hp(Dc) [CPC/Brij-78/Pn/

stability for the formation of w/o microemulsion, the requirement
of Pn depends on its interaction with these surfactants of different
characteristics at different x. In the simplest model, two states of
water present inside the droplet of w/o microemulsions, that is,
interfacial (or bound) water, which displays modified properties
compared with bulk water, and interior (core) water, which be-
have similarly to bulk water [4]. The packing of the amphiphiles
and the accommodation of Pn at the droplet interface are influ-
enced by delocalization of the charge as well as charge shielding
due to the presence of pyridine ring in CPC [25] and the solvation
(hydration) of the polyethylene oxide head groups of Brij-58 or
Brij-78 wherein the head group (C5H5N+H) of CPC resides [51].
Upon the addition of Brij-58 or Brij-78 into CPC based system,
[8.81(5.41)]

[5.19(3.76)]
[6.18(4.01)]

[3.33(3.03)]
[7.80(4.85)]

the electrostatic repulsion between the charged head groups of

6.56(5.56)

4.23(3.52)

2.45(3.11)
5.71(4.05)

5.47(3.90)

ionic surfactant decreases, and consequently, a steric repulsion

Hp(Dc)]

between large POE chains generates. At lower x, long POE chains

of Brij-58 or Brij-78 molecules might be placed covering the head
group of CPC with twisted form due to ion–dipole interaction be-
Kd CPC/Brij-58/Pn/Hp(Dc) [CPC/Brij-78/Pn/

tween ionic (C5H5N+H) and POE of Brij-58 or Brij-78. There is an

additional scope for the formation of hydrogen bond in between
penetrated large fractions of POE chains of Brij-58 or Brij-78
and water molecule in a droplet core [52]. Tasaki [53] suggested
that a water molecule bridged between POE–oxygen separated
by two EO units with hydrogen bonding. The extensive hydrogen
bond network was found, running through the POE helix, and thus
stabilizing the helix. This type of water, which is bound to EO
[32.97(14.46)]

groups or trapped in coils formed by long POE head groups of

[11.61(5.72)]
[22.09(7.05)]

[3.75(3.33)]
[7.85(4.65)]
13.49(9.09)

nonionic surfactant, is known as bound water. As a result, the

9.66(4.98)

8.77(4.27)

5.36(3.94)

2.64(3.44)
Hp(Dc)]

network of delocalized p-electrons of pyridinium ring of CPC

molecules inside the surface of the water droplet is not quite sta-
bilized, because the number of water molecules inside the droplet
core is very small and even charge distribution is impaired. Also,
103noa (mol) CPC/Brij-58/Pn/Hp(Dc) [CPC/Brij-78/Pn/

the motion of helically twisted POE chains of Brij-58 or Brij-78

may be restricted due to the formation of hydrogen bond between
POE and water. In turn, the requirement of Pn at the interface is
gradually increased to fill the gap on large droplet surface and sta-
bilize the water droplet up to certain x (herein x = 30). In light of
molecular interactions between the constituents involved in the
transfer process, it can be stated that there may be three types
of interactions taking place at the interface and inside the water
pool; (i) between CPC and Pn, (ii) between Brij-58 or Brij-78 and
water molecules, and (iii) between CPC and water molecules. It
is quite likely that at lower range of x, first two types of interac-
303 K and XBrij-58 or Brij-78 = 0.2 with varying water content from x = 10 to 50a.

[1.47(2.61)]
[0.96(1.53)]

[3.60(3.78)]
[1.98(3.01)]
[0.81(0.91)]
1.13(1.27)

1.53(1.97)

2.14(2.45)

2.42(2.66)
1.96(2.07)
Hp(Dc)]

5
The error limits of Kd and DG0t are ±2% and ±3%, respectively.
104n1a (mol) CPC/Brij-58/Pn/Hp(Dc) [CPC/Brij-78/Pn/

3
nai /ns

1
[16.69(18.98)]
[14.32(15.98)]

[19.85(21.99)]

[18.61(20.23)]

[6.88(15.18)]
13.98(18.86)

11.62(13.59)

0
8.35(13.51)

9.52(15.02)

2.47(7.69)

10 20 30 40 50
Hp(Dc)]

Fig. 2. Plot of nia =ns vs. x for CPC/Brij-58/Pn/[Hp () or Dc (j)]/water, CPC/Brij-78/
Table 1

10

20

30

40

50

Pn/[Hp (N) or Dc ()]/water w/o microemulsion systems at XBrij-58 or Brij-78 = 0.2 and
x

at constant temperature of 303 K.

100 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
Scheme 1. Pictorial representation of mixed surfactant w/o microemulsions at lower and higher x.
tions predominate over the latter. Consequently, Pn molecule can
accommodate itself more and more at the interface before attain-
ment of a specific x. But after attainment of specific x, the inter-
actions between the constituents change its direction. After a
specific x, a Brij type of surfactant is fully hydrated, and thereby
free or bulk-like water (i.e., having only water-water interactions)
is formed [54]. Then, pyridinium ring of CPC molecules play a sig-
nificant role to stabilize the water/oil interface, as water molecules
inside the droplet core are sufficiently large to meet the charge dis-
tribution arising out of the delocalized p-electrons of pyridinium
ring of CPC molecules. In other words, interaction between CPC
and water molecules inside the droplet core is favorable over
CPC–Pn and Brij–water. It was previously reported that for non-
ionic surfactant after a threshold concentration of alkanol (i.e., Pn
or Hx), three-dimensional network of water about the surfactant
head groups is distorted and thereby detaching the outer weakly
associated water layers [54]. Therefore, with the increase in drop-
let size by the addition of more water, helically twisted POE chain
might be unfolded in absence of strong hydrogen bond and it may
spread over the surface of the water pool. Consequently, it will oc-
cupy large surface area of the droplet and reduce the free surface
area. Hence, mutual accommodation of supporting amphiphile
(Pn) with basic mixed amphiphiles (CPC and Brij-58 or Brij-78) at
the interface of fixed amount ðnia =ns Þ suddenly falls after crossing
a certain level of x (=30) in both oils.
3.1.2. Packing parameter
In this section, the structural features of the micellar aggregates
by the geometry or ‘‘packing’’ properties has been discussed. It has
been observed that nia values are higher for CPC/Brij-58 (or, Brij-
78)/Pn systems (at XBrij-58 or Brij-78 = 0.2) compared to CPC/Pn sys-
tem stabilized in Dc oil (Fig. S2). It is apparent that the presence
of Brij-58 or Brij-78 in the mixed surfactant microemulsion sys-
tems vis-à-vis the interaction of these surfactants with Pn, which
in turn the accommodation of these amphiphiles at the interface,
plays an important role for the formation of these w/o microemul-
sions. Hence, this phenomenon can be understood by the packing
parameter P of the molecular geometry [55]. Israelachvili et al.
[55] defined the dimensionless packing parameter (P) of the
molecular geometry as an index to predict the size and shape of
the micelles. P was defined by vc/(aolc). In general, vc and lc are cal-
culated by Tanford [56]. The ao is determined from the aggregation
number assuming spherical micelles [57] or is approximately esti-
mated with minimum adsorbed area at the interface [58]. The ao
values for CPC and Pn are 0.71 and 0.16 nm2, respectively
[27,32]. On the other hand, the surface area, ao, per surfactant mol-
ecule at the micelle/water interface is difficult to estimate for Brij-
58 and Brij-78, probably due to the presence of helically twisted
POE-chains [59]. However, Schefer et al. described structure of
Brij-58 micelle with a spherical core/shell model by SANS mea-
surement [60]. The optimum head group size of Brij-58 is calcu-
lated dividing the total surface area of the micelle by the
aggregation number [61]. The aggregation number of Brij-58 mi-
celle and the total surface area (calculated from radius of micelle)
are taken from Schefer et al. [60]. On the basis of this model, ao va-
lue is calculated and found to be 1.81 nm2 for Brij-58. As Brij-78
contains same number of POE chains, ao value is assumed to be
1.81 nm2. For mixed surfactant microemulsion systems, P can be
calculated using the relationship proposed by Ninham [62]:
P ¼ ½ðxA v c =ao lc ÞA þ ðxB v c =ao lc ÞB =ðxA þ xB Þ ð14Þ
where xA and xB are the mole fraction of the surfactant A and B pres-
ent at the interface, respectively, and the significance of other
parameters has been mentioned earlier. Thus, we obtain P as 0.30
for CPC and 0.24 for CPC/Brij-58 or Brij-78 (at XBrij-58 or Brij-78 = 0.2)
using Eq. (14). Brij-58 or Brij-78 leads to a more unsuitable P for
CPC/Brij-58 (or, Brij-78) (0.24) compared to single CPC system
(0.30) for reverse aggregate formation due to hydration of the polar
head group (POE). From the theoretical analysis, the smaller P re-
quires larger amount of alkanol populating on the droplet surface
[30]. This agrees well with the experimental results shown in Fig. S2.
The compositional variations (described in the preceding para-
graph) can also be well supported using the concept of Peff for the
mixed film consisting of different surfactants and cosurfactant at
the oil/water interface. Peff can be estimated by the following for-
mula [62]:
 
vc ðX v c =ao lc Þs þ ðX v c =ao lc Þa
Peff ¼ ¼
ao lc eff Xs þ Xa
ðv c =ao lc Þs þ Iðv c =ao lc Þa
¼ ð15Þ
1þI
where X is the mole fraction of the corresponding species at the
mixed film, (vc/aolc)s is the summation of [(vc/aolc)s]A and [(vc/aolc)s]B
for mixed surfactant systems and I come from the dilution experi-
 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
ment. In the present investigation, Peff-values for CPC/Brij-58 or Brij-
78/Pn systems stabilized in Hp and Dc at different x (=10, 20, 30, 40,
50) have been found to be unity (1.00–1.09), which satisfy the
requirement of reversed aggregate formation. This indicates that
the cosurfactant Pn fills the gaps among the surfactant molecules
on the droplet surface and leads to the formation of stable mixed
surfactant w/o microemulsions.
3.1.3. Effect of water content (x) on bulk oil compositions ðnoa Þ
From Tables 1, it is clearly evident that noa increases with
increasing x in both oils. This can be argued as follows. The inter-
droplet interaction becomes more attractive as well as droplet size
increases significantly, with increasing x. As droplet size increases,
more oil molecules come inside the droplet core and thereby no in-
creases [63]. In order to maintain constant value of ko (which is
equal to noa =no ) at a given temperature, noa has to be increased, that
is, more Pn molecules get accommodated in the oleic phase. Simi-
lar trend for noa have also been reported earlier [27,30,32]. Further,
it has been observed that noa is increased with increase in oil chain
length at each x for all these systems. As the solubility of Pn in the
oil phase decreases with increase in oil chain length, the quantity
of Pn necessary to stabilize the system composed of Hp is smaller
as compared to Dc [32]. Hence, noa increase with increase in oil
chain length. It also reveals from Fig. 2 that nia increases with in-
crease in oil chain length at each x for all these systems, thus con-
firming that the Pn is more transferred to the interface as its
solubility in the oil phase decrease [32]. It may be indicated that
the partitioning of alcohols at the interface is favored for higher
chain length of oils [32]. Similar results using oils of different chain
lengths were also reported earlier [26,32,38,42].
3.2. Thermodynamics of transfer of alkanol (Pn) from oils (Hp and Dc)
to the interface
In this section, analysis of the transfer of Pn from oleic phase to
the interface of mixed surfactant (ionic + nonionic) w/o micro-
emulsions using dilution experiments from thermodynamic point
of view is presented, which is seldom reported [38]. Such reports
for w/o microemulsions stabilized in hydrocarbons and
hydrophilic oil using single surfactant are available in literature
[26,27,29–35,37,42]. Thermodynamic parameters (Kd, DG0t ;
DH0t ; DS0t and ½ðDC 0p Þt ) for the transfer of Pn from the continuous
oil phase (Hp or Dc) to the interfacial region of mixed surfactants
(CPC + Brij-58 or Brij-78) with varying x (10 ? 50) at a fixed
XBrij-58 or Brij-78 = 0.2 and temperature (303 K) (Section 3.2.1) and
at a fixed x (=50) with varying XBrij-58 or Brij-78 (0 ? 1.0) and tem-
peratures (293, 303, 313, and 323 K) (Sections 3.2.2, 3.2.3, 3.2.4,
3.2.5, 3.2.6) have been evaluated according to Eqs. (7)–(13). The
data are presented in Table 1 and Tables 2A and 2B. Representative
plots of – DG0t vs. XBrij-58 or Brij-78 for CPC/Brij-58 or Brij-78/Pn/Dc/
water and DH0t or DS0t vs. XBrij-78 for CPC/Brij-78/Pn/Hp or Dc/water
at four different temperatures are illustrated in Figs. 3–5. Similar
plots for other systems are provided in Supplementary material
section (Figs. S3 and S4). DG0t values are negative at all composi-
tions (XBrij-58 or Brij-78 = 0 ? 1.0) and temperatures in both oils;
hence, spontaneous formation of w/o microemulsions is suggested.
Both similar and dissimilar trends in all these energetic parameters
at comparable physicochemical environments are reported
[26,32,35,38,42].
The deciphering of different phenomena that guide the overall
thermodynamics of the transfer of Pn to the interface is worth-
while but complex. However, an attempt has been made to present
a comprehensive accounting of the experimental results.
101
3.2.1. Effect of x on DG0t of transfer process
It is evident from Table 1 that the values of DG0t , which is
indicative of spontaneity of the alkanol transfer process (Pnoil ? P-
nint), decrease with increasing x (=10–50) for all these w/o micro-
emulsion systems. With increasing x, the droplet is swollen and
thus the interfacial curvature is decreased. As a result, the surfac-
tant molecules are accommodated more closely at the interface
and decrease the gaps, resulting from the unsuitable molecular
geometry of the surfactants. Hence, the trend of transferring of
Pn from oil to the interface is weakened. Again, with increasing
x, the relative retention of Pn in oil has become more (as reflected
from values of noa , Table 1) than its transfer to the interface. In other
words, association between surfactant and cosurfactant molecules
at the interface becomes less favorable with increase in x. This
type of variation was reported by Hait and Moulik [27], Zheng
et al. [30,31], and Paul et al. [32].
It has been observed that CPC/Brij-78 mixed system is more
spontaneous than CPC/Brij-58 system at comparable physicochem-
ical environments in both oils. The nonionic surfactant with longer
hydrocarbon chain possesses higher efficiency to change the
hydrophilicity, making the interfacial layer effectively more hydro-
phobic. Also, the larger bending elastic modulus of the interfacial
layer arising out of the longer chain of the nonionic surfactant
leads to larger solubilization ability. These two effects determine
the higher efficiency of nonionic surfactant with longer hydrocar-
bon chain to form w/o microemulsions [39]. Hence, the effective
binding between Pn and CPC at the interface increases in the order:
CPC/Brij-58 < CPC/Brij-78, which corroborates well with the degree
of spontaneity of the transfer process.
In comparison, DG0t values are more negative in Hp continuum
than in Dc, indicating the transfer process to be more favorable
for the former than the latter. Similar observations were reported
by Digout et al. [26] and Paul et al. [32] for w/o microemulsions
stabilized by single surfactant of different charge types and sizes
of the polar head group. It is quite likely that the interfacial fluidity
is likely to increase with increasing oil chain length and increasing
alcohol partitioning at the interface ðnia Þ (Table1). Such an increase
in interfacial fluidity results in inelastic collisions between drop-
lets, leading to formation of transient dimmers and an enhanced
apparent interdroplet interaction for Dc based systems. At suffi-
ciently strong interdroplet interaction, the microemulsion droplets
stabilized in Dc are less stabilized compared to Hp based systems
[64].
3.2.2. Effect of Xnonionic and temperature on DG0t of transfer process at a
fixed x
It can be seen from Tables 2A and 2B that the spontaneity of the
transfer of Pn from oil (Hp or Dc) to the interface for pure CPC sta-
bilized system increases with increasing temperature in Hp (ex-
cept at 303 K, where a minimum value of DG0t (4.03 kJ ml1) is
observed), whereas spontaneity decreases with increasing temper-
ature in Dc. This trend corroborates well with our previous report
on CPC stabilized systems in Dc (or, Dd) with Pn used as alkanol
[32] and Moulik et al. [42] and Digout et al. [26] for water/CPC/alk-
anol/alkanes (C6 and C7) and water/CPC/alkanols (C4–C6)/alkanes
(C5 and C8–C10) w/o microemulsion systems, respectively. The
spontaneity of pure Brij-58 or Brij-78 stabilized microemulsion
systems increases with increasing temperature in both oils, which
agrees well with our previous reports [32,38] and Mehta et al. [35].
It is evident from Tables 2A and 2B and representative plot of -
DG0t vs. XBrij-58 or Brij-78 at four temperatures in Dc (depicted in
Fig. 3) that the DG0t values are not straightforward at mixed compo-
sitions (i.e., XBrij-58 or Brij-78 = 0.2–0.8). DG0t values increase with in-
crease in temperature (293, 313, and 323 K) at all compositions for
CPC/ Brij-58 or Brij-78 systems stabilized in Hp. However, excep-
tional feature, that is, lowest values of DG0t have shown in the
 102
Table 2A
Interfacial and bulk compositions of 1-pentanol, distribution constant and thermodynamic parameters of its transfer from heptane and decane to the interface for w/o microemulsion containing 2 ml oil, 0.5 mmol of surfactant and at a
fixed x = 50 with varying temperature from 293 to 323 K.a (SYSTEM: CPC/Brij-58/Pn/oil/water).

XBrij-58 T (K) 104 n1a (mol1) Hp(Dc) 103n0a (mol1) Hp(Dc) Kd Hp(Dc) DG0t (kJ mol1) Hp(Dc) DH0t (kJ mol1) Hp(Dc) DS0t (J K1 mol1) Hp(Dc)
0.0 293 5.55(8.35) 1.57(2.39) 6.97(3.95) 4.73(3.35) 10.99(12.72) 53.68(31.97)
303 4.27(7.38) 1.87(2.67) 4.94(3.38) 4.03(3.07) 8.67(14.50) 15.68(37.74)
313 9.22(5.91) 1.47(2.84) 9.36(2.88) 5.82(2.75) 28.99(16.35) 74.05(43.46)
323 12.64(4.91) 1.40(3.11) 10.99(2.40) 6.43(2.36) 49.98(18.26) 134.85(49.23)
0.2 293 3.61(8.28) 2.03(2.51) 4.05(3.75) 3.40(3.22) 33.20(9.37) 124.93(42.96)
303 2.47(7.69) 2.42(2.66) 2.64(3.44) 2.45(3.11) 3.40(8.89) 19.32(39.60)

K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
313 4.06(6.50) 2.35(2.95) 3.67(2.99) 3.38(2.85) 27.39(8.39) 76.72(35.61)
323 7.35(5.85) 2.23(3.02) 5.18(2.70) 4.42(2.67) 59.19(7.89) 169.58(32.69)
0.4 293 5.49(9.33) 2.30(2.49) 4.39(3.93) 3.60(3.34) 20.26(19.66) 81.43(78.49)
303 2.44(8.24) 2.63(2.69) 2.39(3.47) 2.20(3.14) 7.75(10.72) 18.33(45.73)
313 9.05(7.16) 2.14(2.89) 5.90(3.07) 4.62(2.92) 36.70(1.48) 102.50(14.05)
323 12.19(6.89) 2.09(2.97) 6.63(2.55) 5.08(2.33) 66.59(8.06) 190.45(14.66)
0.5 293 8.58(8.89) 2.52(3.97) 4.74(3.03) 3.79(2.69) 50.07(1.93) 183.80(15.77)
303 5.39(9.69) 3.19(3.32) 6.05(3.28) 3.03(2.99) 19.07(1.05) 77.89 (6.41)
313 9.42(10.73) 2.80(2.89) 8.18(3.45) 4.47(3.22) 12.95(4.13) 23.92(2.90)
323 10.64(12.13) 2.53(2.75) 4.99(4.03) 5.12(3.74) 46.03(7.31) 129.75(11.05)
0.6 293 5.44(5.85) 2.80(3.41) 2.56(1.95) 3.09(1.63) 25.01(15.26) 95.92(46.52)
303 2.17(6.84) 2.93(3.30) 1.97(2.49) 1.70(2.29) 4.78(17.05) 10.18(48.70)
313 8.03(8.60) 2.41(2.93) 4.11(3.26) 3.44(3.07) 35.58(18.89) 100.46(50.56)
323 11.24(12.52) 2.35(2.48) 5.17(4.20) 4.45(3.86) 67.38(20.80) 193.92(54.85)
0.8 293 7.28(8.36) 5.82(6.38) 2.66(1.98) 2.38(1.66) 13.44(21.02) 53.98(77.39)
303 9.08(10.40) 5.18(5.97) 2.65(2.36) 2.45(2.16) 0.27(15.65) 6.24(59.75)
313 9.88(12.76) 4.92(5.14) 3.15(2.69) 2.99(2.58) 14.44(10.11) 37.89(41.85)
323 13.92(15.63) 4.24(4.66) 3.58(3.39) 3.43(3.28) 29.07(4.39) 79.84(24.19)
1.0 293 7.40(9.26) 5.09(2.95) 3.32(2.36) 2.92(2.09) 8.85(4.25) 37.34(24.48)
303 9.57(10.69) 4.68(2.91) 3.54(2.79) 3.18(2.58) 5.87(3.96) 27.89(23.55)
313 10.65(11.78) 4.48(2.89) 3.66(2.99) 3.38(2.85) 2.79(3.65) 18.03(22.45)
323 13.77(13.21) 4.45(2.85) 3.84(3.24) 3.62(3.16) 0.39(3.33) 8.57(21.52)
a
The error limits of Kd and DG0t , DH0t and DS0t are ±2%, ±3%, ±5%, and ±8%, respectively.
Table 2B
Interfacial and bulk compositions of 1-pentanol, distribution constant, and thermodynamic parameters of its transfer from heptane and decane to the interface for w/o microemulsion containing 2 ml oil, 0.5 mmol of surfactant and at a
fixed x = 50 with varying temperature from 293 to 323 K.a (SYSTEM: CPC/Brij-78/Pn/oil/water).

XBrij-78 T (K) 104 nia (mol) Hp(Dc) 103noa (mol) Hp(Dc) Kd Hp(Dc) DG0t (kJ mol1) Hp(Dc) DH0t (kJ mol1) Hp(Dc) DS0t (J K1 mol1) Hp(Dc)
0.0 293 5.55(8.35) 1.57(2.39) 6.97(3.95) 4.73(3.35) 10.99(12.72) 53.68(31.97)
303 4.27(7.38) 1.87(2.67) 4.94(3.38) 4.03(3.07) 8.67(14.50) 15.68(37.74)
313 9.22(5.91) 1.47(2.84) 9.36(2.88) 5.82(2.75) 28.99(16.35) 74.05(43.46)
323 12.64(4.91) 1.40(3.11) 10.99(2.40) 6.43(2.36) 49.98(18.26) 134.85(49.23)
0.2 293 8.60(20.97) 3.40(3.06) 4.45(3.99) 3.64(3.38) 12.69(3.83) 55.73(1.56)
303 6.88(15.18) 3.60(3.78) 3.75(3.33) 3.33(3.03) 12.63(11.58) 52.67(28.23)

K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
313 10.07(13.63) 3.38(3.98) 4.22(2.92) 3.65(2.79) 12.57(19.59) 49.88(53.69)
323 12.65(8.60) 3.05(4.16) 4.74(2.04) 3.91(1.91) 12.51(27.86) 47.09(80.33)
0.4 293 11.92(28.76) 3.05(2.91) 5.23(4.40) 4.03(3.61) 17.85(16.87) 74.66(45.26)
303 9.22(14.63) 3.72(2.98) 4.02(3.80) 3.51(3.36) 11.29(18.06) 48.84(48.51)
313 12.88(13.24) 3.68(4.43) 4.76(2.57) 3.95(2.46) 4.51(19.29) 25.44(53.79)
323 13.78(10.33) 3.44(4.50) 5.29(2.21) 4.26(2.13) 2.48(20.57) 2.72(57.08)
0.5 293 15.43(15.87) 5.18(5.40) 2.44(2.34) 2.18(2.07) 23.44(11.05) 87.42(30.64)
303 17.07(19.67) 3.69(3.74) 3.38(3.19) 3.07(2.92) 23.02(15.22) 86.10(40.57)
313 19.58(21.66) 2.87(3.04) 4.52(3.68) 3.92(3.23) 22.59(19.53) 84.70(53.04)
323 21.07(24.78) 2.58(2.79) 5.95(4.53) 4.79(4.06) 22.14(23.98) 83.38(61.69)
0.6 293 16.18(19.26) 5.78(7.01) 2.45(2.25) 2.18(1.97) 19.01(7.85) 72.32(33.51)
303 17.39(20.98) 3.98(5.18) 3.28(3.04) 2.99(2.80) 18.89(21.96) 72.23(63.21)
313 18.62(23.33) 3.94(4.04) 4.45(3.51) 3.88(3.14) 18.77(52.76) 72.37(159.12)
323 20.06(25.54) 1.51(2.80) 5.77(8.55) 4.71(5.76) 18.64(84.56) 72.28(243.91)
0.8 293 17.08(19.83) 6.03(7.40) 2.36(2.20) 2.09(1.92) 39.57(6.90) 142.19(17.01)
303 18.49(24.89) 4.13(4.63) 3.69(2.98) 3.29(2.75) 33.01(14.65) 119.81(39.28)
313 21.02(30.50) 3.81(3.12) 5.27(3.29) 4.32(3.10) 26.23(22.66) 97.63(62.49)
323 24.96(31.15) 2.38(2.51) 6.60(5.27) 5.07(4.46) 19.24(30.93) 75.25(81.93)
1.0 293 24.07(25.60) 5.53(5.02) 3.36(2.76) 3.12(2.47) 29.05(39.46) 108.49(143.13)
303 30.52(34.56) 4.40(3.01) 4.52(4.20) 3.80(3.61) 25.48(27.54) 96.01(103.44)
313 32.99(35.99) 3.06(2.38) 5.79(5.14) 4.57(4.41) 21.78(15.22) 83.67(63.23)
323 34.34(37.69) 2.57(2.31) 6.68(6.54) 5.10(5.04) 17.97(2.50) 71.23(23.53)
a
The error limits of Kd and DG0t , DH0t and DS0t are ±2%, ±3%, ±5%, and ±8%, respectively.

103
104 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110

CPC/Brij-58 CPC/Brij-78

-ΔG0t (kJ mol-1)

-ΔG0t (kJ mol-1)

X Brij-58 X Brij-78

Fig. 3. Plot of DG0t vs. XBrij-58 or Brij-78 for CPC/Brij-58 or Brij-78/Pn/Dc/water w/o microemulsion systems at temperatures 293, 303, 313 and 323 K with constant x (=50).

80
60 293K Hp 293K Dc
303K 303K
40 313K 40 313K
323K 323K

Δ H0t (kJ mol-1)

Δ H0t (kJ mol-1)

20
0
0 0.2 0.4 0.6 0.8 1
0
0 0.2 0.4 0.6 0.8 1 -40
-20
-80
-40

-60
XBrij-78 -120 XBrij-78

Fig. 4. Plot of DH0t (kJ mol1) vs. XBrij-78 for CPC/Brij-78/Pn/Hp or Dc/water w/o microemulsion systems at temperatures 293, 303, 313, and 323 K with constant x (=50).

200 293K Hp 200 Dc

293K
303K
303K
313K
100 313K
100 323K
ΔS0t (J K-1 mol-1)

ΔS0t (J K-1 mol-1)

323K

0
0 0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1 -100

-100
-200

X Brij-78
-200 -300
X Brij-78

Fig. 5. Plot of DS0t (J K1 mol1) vs. XBrij-78 for CPC/Brij-78/Pn/Hp or Dc/water w/o microemulsion systems at temperatures 293, 303, 313, and 323 K with constant x (=50).

range of XBrij-58 = 0.2–0.6 and XBrij-78 = 0.2–0.4 at 303 K. Similar
trend was also reported by Moulik et al. [42] for water/CPC/alka-
nol/alkane (C6 and C7) and Digout et al. [28] for water/CPC/alkanol
(C4–C6)/alkane (C5 and C8–C10) systems. On the other hand, a
regular decreasing trend in DG0t value with temperature has
been observed up to XBrij-58 or Brij-78 = 0.4; thereafter, (i.e., at
XBrij-58 or Brij-78  0.45) trend is reversed for both CPC/Brij-58 and
CPC/Brij-78 systems stabilized in Dc. Similar trend in variation of
DG0t with temperature in the vicinity of equimolar composition
was reported for mixed surfactant microemulsion systems
(CTAB/Brij-58/Bu or Pn/Hp or Dc/water) [38]. Apart from interde-
pendence of DG0t on composition and temperature, result shows
that the chain length of both Brij-58 or Brij-78 and oils influence
DG0t , is presented in subsequent sections.
3.2.3. Effect of chain length of nonionic surfactant
It is evident from Tables 2A and 2B that DG0t values show no
regular trend at lower XBrij-58 or Brij-78 (=0.2, 0.4, and 0.5) for CPC/
Brij-58 and CPC/Brij-78 systems in both oils; whereas, at higher
XBrij-58 or Brij-78 (=0.6, 0.8 and 1.0), DG0t values of the latter are lar-
ger than the former at the studied temperature range. So, the spon-
taneity of the transfer process of Pn increases with increase in
chain length of nonionic surfactant at higher mixing ratios. Similar
trend in the spontaneity of the alkanol transfer process was re-
ported by De et al. [34] for CnTAB, where n = 10, 14, 16 or PS 40
or PS 60 or PS 80]/Bu/Hp/water microemulsion system.
3.2.4. Effect of oil chain length
DG0t values are more negative in Hp continuum than Dc contin-
uum at all compositions of the mixed surfactant microemulsions,
indicating the process to be more favorable for the former than
the latter. It is suggested an effective binding (or a strong interac-
tion) between amphiphiles (CPC/Brij-58 or Brij-78) and alkanol
(Pn) at the interface, indicating spontaneity of the transfer process
becomes more favored in lower chain length of oils. Similar obser-
vations were reported by Moulik et al. [42], Paul et al. [32], and
 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
Mitra et al. [38]. From Tables 2A and 2B, it reveals that the values of
DG0t become more negative with increase in temperature for
(CPC + Brij-58 or Brij-78) in Hp system in pure and mixed compo-
sitions and (CPC + Brij-78) in Dc system at XBrij-78 P 0.5. It is sug-
gested that the transfer process (Pnoil ? Pnint) is favored at
higher temperatures in both oils at all compositions, except at low-
er mole fraction of Brij-78 (XBrij-78 6 0.4).
3.2.5. Effect of Xnonionic and temperature on DH0t and DS0t of transfer
process
Due to nonlinear dependence of ðDG0t =TÞ on 1/T in terms of
a two degree polynomial equation, at each composition of a
nonionic surfactant (Xnonionic) (Fig. S1), four values of DH0t and
DS0t at four temperatures have been evaluated and are presented
in Tables 2A and 2B. The profile of DH0t and DS0t with composition
(XBrij-58 or Brij-78) and temperature [Fig. 4 and 5 and Figs. S3 and S4
(supplementary material)] is not straightforward upon the
addition of nonionic surfactant(s) (Brij-58 or Brij-78 with cetyl
and stearyl nonpolar tail, respectively) to the ionic surfactant
(CPC with cetyl nonpolar tail) under various physicochemical
environments (as mentioned earlier).
For pure CPC system, overall transfer process is exothermic at
all experimental temperatures with negative entropy change (or-
der) in both oils. So, Pn causes release of heat during transfer pro-
cess. Consequently, the negative entropy change is due to more
organization of the interface and its surroundings. Therefore, the
interface composed of Pn and CPC is to some extent orderly. Such
negative enthalpy and entropy changes were observed by Digout
et al. [26] for CPC derived systems stabilized in different chain
length of cosurfactants (Bu, Pn, Hx) and oils (pentane/octane/dec-
ane). For pure Brij-58 or Brij-78 stabilized system, the process is
endothermic with absorption of heat at all experimental tempera-
tures with positive entropy change (disorder) in both oils. The non-
ionic surfactant produces insignificant ion-dipolar effect with the
alkanol showing endothermic transfer from bulk oil to the inter-
face [33]. The desolvation of head group of Brij-58 or Brij-78 during
the transfer of Pn in the oil is responsible for both positive enthalpy
and entropy change [38]. Opposite behavior toward temperature
for ionic and nonionic surfactants might be responsible for such
trend of enthalpy and entropy values with temperature [65,66].
However, the magnitudes of DH0t and DS0t in pure Brij-78 stabilized
system are higher than pure Brij-58 system in both oils. The differ-
ence in enthalpic and entropic behaviors between Brij-58 and Brij-
78 systems in both oils may be due to the difference in chain length
between two nonionic surfactants; the latter becomes more endo-
thermic and disordered than the former.
At compositions in between these two extremes (i.e.,
XBrij-58 or Brij-78 = 0.2 ? 0.8) in both oils, the transfer process evi-
denced a single athermal point [for CPC/Brij-78/Pn/Hp or, Dc/water
at 303 and 313 K (Fig. 4)] as well as a couple of athermal points (for
CPC/Brij-78/Pn/Hp or Dc/water at 323 K and 293 K, respectively
(Fig. 4), CPC/Brij-58/Pn/Dc/water at all studied temperatures
(Fig. S3) and CPC/Brij-58/Pn/Hp/water at 303 K (Fig. S3)), indicating
changes from exothermicity to endothermicity or vice versa in
both oils. Significant crossing over from one energetic process to
another, that is, DH0t ¼ 0 indicates that the driving force for Pn
transfer process is entropically controlled [67]. Mixed ionic-non-
ionic surfactant derived athermal microemulsion formulation
[CTAB/Brij-58/Bu or Pn/Hp (or Dc)/water] was reported earlier
[38]. Both positive DH0t and DS0t at lower mole fractions of Brij-58
(XBrij-58 < 0.5) and both negative DH0t and DS0t at higher mole frac-
tions of Brij-58 (XBrij-58 > 0.5), that is, a single crossing over in the
close proximity of XBrij-58 = 0.5 was observed [38].
From Fig. S3, it can be seen that the DH0t values for CPC/Brij-58
derived system are both positive (exothermic) and negative (endo-
thermic) at the studied temperature range in both oils. However,
105
enthalpy of the transfer process has been found to be endothermic
for CPC/Brij-78 system stabilized in Hp, whereas the process is exo-
thermic in Dc (Fig. 4). The plot of DS0t vs. XBrij-58 or Brij-78 has been
found to be replica of corresponding DH0t vs. XBrij-58 or Brij-78 plots
for comparable systems (Fig. 5 and Fig. S4). Further, it has been ob-
served that DS0t values are both positive (disorder or randomness)
and negative (order or organize) in both oils at XBrij-58 = 0.2–0.8 for
CPC/Brij-58 derived system, whereas DS0t values are positive and
negative in Hp and Dc, respectively, at XBrij-78 = 0.2–0.8 for CPC/
Brij-78 derived system. Thus, the difference in entropic behavior
between Hp and Dc continuum may due to the chain length differ-
ence between the two oleic phases; the latter becomes less disor-
dered than the former, as reported earlier [38].
An interesting feature reveals from the Tables 2A and 2B and
Figs. 4, 5 and Figs. S3 and S4 that both DH0t and DS0t values decrease
with increase in temperature for all these microemulsion systems
in pure and mixed compositions. However, insignificant changes in
these parameters with temperature have been observed at certain
compositions (at XBrij-58 = 0.2, 1.0 and XBrij-78 = 0.2, 0.5, 0.6 for CPC/
Brij-58/Pn/Dc and CPC/Brij-78/Pn/Hp systems, respectively), lead-
ing to the formation of isenthalpic and isentropic microemulsion
systems. It can be argued that the surfactant head group of the
nonionic surfactant is more dehydrated than the hydrophobic tail
with the increase in temperature, which leads to overall ordering
(negative entropy, DS0t ) of the system [68]. Further, DS0t suggests
that both entropy as well as enthalpy are involved in the transfer
process [67]. Consequently, microemulsion compositions with lar-
ger DH0t values (more exothermic) results in larger DS0t values
(ordered), that is, greater interaction between the constituents at
the interface, leads to more ordered interface due to transfer of
Pn (Pnoil ? Pnint) [69]. In addition, it can be argued for negative en-
tropy, DS0t that during formation of nanodroplets in w/o micro-
emulsions, the penetration of water into the oil/amphiphile
continuum forming cavity and subsequent organization of the
amphiphiles at the droplet interface resulted in an increase in
overall order with negative entropy of the multicomponent system
[70]. It is apparent that different phenomena associated with the
transfer process, viz., changing aggregation number, solvation–
desolvation of nonionic surfactants, electrostatic and steric interac-
tion between hydrophilic head group of CPC, steric and other non-
specific processes contribute their shares to the DH0t and DS0t [71].
Hence, it can be inferred that the overall mixed surfactant
microemulsion forming systems can end up with both absorption
or release of heat and with ordered or disordered state, depending
on their chemical compositions (i.e., the constituent surfactant(s)
with their configuration, content, and type of oil) and thermal
condition.
Since DH0t became a function of temperature, the ðDC 0P Þt values
have also been obtained at all compositions for both systems from
the slope of the plots of DH0t vs. T (depicted in Supplementary
material, Fig. S5) according to Eq. (13). All these values are negative
(presented in Supplementary material (Table S1)) and agree well
with those reported by Mitra et al. [36] for C2/Hx/i-Oc/water
microemulsion system. Such negative values are usually observed
for the self-association of amphiphiles and can be attributed to the
removal of large areas of nonpolar surface from contact with water
on formation of reverse micelles [72]. It has been observed that
ðDC 0P Þt tends to zero at XBrij-58 = 0.2, 1.0 and XBrij-78 = 0.2, 0.5, 0.6
for CPC/Brij-58/Pn/Dc and CPC/Brij-78/Pn/Hp systems, respec-
tively, which corroborates well with profile of DH0t and DS0t vs.
XBrij-58 or Brij-78 at different temperatures (Figs. 4, 5 and Figs. S3
and S4) discussed in preceding paragraph. Kunz et al. [73] reported
that formation of temperature-insensitive microemulsions are
important for some practical purposes (e.g., for formulation of
product), whereas for other applications, such as for extraction
and purification process or organic synthesis, the temperature
106 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
dependence of microemulsions can be desirable. The present re-
port on mixed surfactant microemulsion systems provides such a
wide compositions in which both temperature dependent and
independent formulations can be found.
3.2.6. Correlation between DH0t and DS0t
In kinetics and equilibrium studies, an extra thermodynamic
linear correlation between DH0t and DS0t changes for the involved
process is often reported, called the enthalpy–entropy compensa-
tion effect, and such a phenomenon has been observed to be valid
also for micelle and microemulsion forming systems
[27,32,35,38,42]. In general, the compensation effect can be de-
scribed by a liner relationship in the form [74]:
DH0t ¼ T comp  DS0t þ DðH0 Þt ð16Þ
where Tcomp, is the slope of the compensation plot and DðH0 Þt , the
intrinsic enthalpy change of Pn transfer process is the intercept.
According to the working scheme of Lumry and Rajender [74] for
a compensation phenomenon, the micellization or microemulsifica-
tion can be described as consisting of two-part processes: (a) the
‘‘desolvation’’ part, that is, the dehydration of the hydrocarbon tail
or polar head of surfactant molecules, and (b) the ‘‘chemical’’ part,
that is, aggregation of the hydrocarbon tails or polar head of surfac-
tant molecules to form micelle or reverse micelle. Tcomp can be inter-
preted as a characteristic of solute–solute and solute–solvent
interactions, that is, proposed as a measure of the ‘‘desolvation’’
part. DðH0 Þt characterizes the solute–solute interaction, that is, con-
sidered as an index of the ‘‘chemical’’ part. The thermodynamic re-
sults herein collected were tested for this correlation and illustrated
as representative plots for CPC/Brij-58 or Brij-78/Pn/Hp or Dc/water
at 303 K (Fig. 6A and B). A good linear correlation was observed at
the temperature of measurement (regression coefficients are
0.9961 and 0.9997), that is, mutual compensation temperature of
295 K and 301 K, which was lesser by 8 K and 2 K than the temper-
ature of measurement (303 K), respectively. Tcomp and DðH0 Þt ob-
tained at different experimental temperatures (293, 303, 313 and
323 K) for these systems are presented in Supplementary material
(Table S2). Tcomp temperatures are slightly deviated from the exper-
imental temperatures. Such a deviation is quite common in litera-
ture [26,27,38,42]. In our previous reports [32,38], the
discrepancy between experimental and compensation tempera-
tures were elaborately discussed. Further, it reveals from Table S2
that the values of DðH0 Þt lie in the range of 2.67 kJ/mol to
4.01 kJ/mol. DðH0 Þt decreases with increase in experimental tem-
perature for CPC/Brij-58 (or, Brij-78) systems in both oils. There ex-
ists an equilibrium between (free water in bulk solvent + free
surfactant molecules with associated water and solvent molecules)
and (surfactants with associated water and solvent molecules in the
reverse micelles + released solvent molecules). Increasing experi-
mental temperature weakens molecular interactions which results
in shifting the surfactant monomer-reverse micelle equilibrium to-
ward the monomer that affects aggregation of surfactant molecules
as well as DðH0 Þt [75]. It has been observed that DðH0 Þt decreases
with an increase in hydrophobic chain length of nonionic surfactant
(C16 or C18) in mixed systems. This trend can be attributed to the in-
crease in hydrophobic chain, which leads to an increase in steric
hindrance in the formation of reverse micelles that manifests itself
in a decrease in the value of the intercept DðH0 Þt [76].
The aforesaid analysis of the thermodynamics of the studied
transfer process can be summarized as follows: DG0t consists of a
number of factors, which may account respectively for the transfer
of surfactants (CPC and Brij-58 or Brij-78) and Pn tails from water to
the interfacial film, the deformation of the tails to satisfy packing
constraints, the free energy of formation of the oil/water interface,
the steric and ionic interactions between the head groups of CPC as
well as interaction arising out of dissimilar head groups of both CPC
and Brij-58 or Brij-78, the free energy of mixing of surfactants, Pn,
and oil (Hp or Dc) in the film region [77], and free energy due to for-
mation of hydrated nonionic surfactant (Brij-58 or Brij-78) results
in formation of different states of water in the pool [4,78]. As a re-
sult of these possible contributions toward DG0t at different temper-
atures, heat involving processes and consequently conformational
entropy due to packing restrictions of the hydrocarbon chains,
and entropy of mixing the two surfactants in the aggregates make
the thermodynamics more complex. Such a comprehensive analy-
sis on the formation and stability of w/o mixed surfactant micro-
emulsions based on ‘‘Bowcott and Schulman model’’ [22] from
the view point of thermodynamics is not found in literature. Further
studies along these series of measurements are in progress to shed
more quantitative description of these thermodynamic quantities
in quaternary w/o mixed surfactant microemulsions.
3.3. Structural parameters of mixed surfactant microemulsion droplets
In this section, structural parameters (viz. Rw, Re, dI (i.e., Re–Rw),
Nd, N s , and N a ) for (CPC + Brij-58 or Brij-78)/Pn/Hp or Dc/water
microemulsions at different physicochemical environments with
varying x (10–50) at a fixed composition (XBrij-58 or Brij-78 = 0.2)
and at 303 K is presented. These parameters have been evaluated
on the basis of a structural model (after incorporating suitable
modifications in view of the mixed surfactant microemulsion sys-
tems) followed by different equations as well as the results derived
from dilution experiments and are provided in the Supplementary
material (Section 2). The results are presented in Table 3. The de-
rived values are not experimental data and depend strongly on
the assumptions made in the calculations. However, general con-
clusions on the trend of variation of these structural parameters
at different physicochemical environments can be drawn from
these values. Such a study using mixed surfactant w/o microemul-
sions is not reported earlier. Very recently, we have reported that
Re or droplet size (dh) of (CTAB + C16E20)/Bu (or Pn)/Hp or Dc/water
w/o microemulsion systems at equimolar composition increases
with increase in x from both theoretical calculations and dynamic
light scattering, DLS measurements, which showed an average of
18% higher compared to that obtained from theoretical calcula-
tions based on interfacial composition [50].
3.3.1. Effect of x
It is evident from Table 3 that the Re and Rw increase with
increasing water content (x) for all the systems. The values of Re
are higher than Rw in all the cases. These trends agree well with
previous reports on single surfactant (similar or dissimilar with
present report) derived w/o microemulsions [26,30–34]. The aver-
age values of Re/Rw are 1.40 and 1.44 for Hp and Dc stabilized sys-
tems respectively, at the studied x range. According to previous
reports, the average value of Re/Rw lies in between 1.16 and 1.38
for single surfactant microemulsions [26,32]. This slight increase
in Re/Rw ratios may be attributed to the formation of mixed inter-
facial film wherein tails of nonionic surfactant(s) contribute. In the
present study, Re and Rw values are found to be 3.51 and 2.10, and
7.09 and 6.07, respectively, for CPC/Brij-58/Hp system and the cor-
responding values for CPC/Brij-58/Dc systems are 3.49 and 2.00,
and 6.56 and 5.47 nm at x = 10 and 50, respectively. On the other
hand, Re and Rw values are found to be 3.50 and 1.99, and 6.66 and
5.57, respectively, for CPC/Brij-78/Hp system and the correspond-
ing values for CPC/Brij-78/Dc systems are 3.48 and 1.97, and 6.04
and 4.87 nm at x = 10 and 50, respectively. The extent of variation
of Rw lies in between 2.90 nm and 3.97 nm, that is, an average of
3.44 nm for all the systems at the studied x range. Similar varia-
tion of Rw with increasing x (at comparable x range used in the
present report) is reported for single surfactants (CPC, CTAB, SDS,
 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
25
Hp
20
Dc
15
10
Δ H 0t (kJ mol-1)
0
-60 -40 -20 0 20 40
-5
R2 = 0.9961
-10
Tcomp = 294.5K
-15
-20
Fig. 6. Enthalpy–entropy compensation plot for (A) CPC/Brij-58/Pn/Hp (or, Dc)/water; (B) CPC/Brij-78/Pn/Hp (or, Dc)/water w/o microemulsion systems at 303 K.
Brij-35, and C12-s-C12.2Br) stabilized in oils (both hydrocarbons
and isopropyl myristate) [27,30,32]. But the degree of variation
of Rw, depends on the type of surfactant, cosurfactant, and oil used.
According to these reports, the adjustable radius of the water pool
(Rw) is useful for preparing metal nanoparticles of different sizes
using w/o microemulsions as templates [30–32]. It can be further
noted that mixed surfactant microemulsions yield smaller Rw
((2.00–5.47 nm) for CPC + Brij-58/Pn/Dc/water system and (1.97–
4.87 nm) for CPC + Brij-78/Pn/Dc/water system) compared to
(2.27–6.33 nm) CPC/Pn/Dc/water system at x (=10–50) and
303 K [32]. Hence, the present report further substantiates that
the addition of Brij-58 or Brij-78 to CPC modulates the dimension
of the water pool, wherein most of the reactions occur, depending
upon their contents. In reversed aggregates, the oxyethylene
groups are located on the surface of the water pool, which probably
affects the compositions of the mixed film and the size of the
aggregates [79].
Further, it has been observed from Table 3 that dI (i.e., interfa-
cial thickness is an important physical property which provides
quantitative measure for the size of the interface [80]) decreases
with increase in x, as the increase in Rw is much greater in compar-
ison with the increase in Re under comparable water content for all
these systems. It can be argued as follows. With increasing x, the
w/o microemulsion system may gradually turned toward the o/w
microemulsion system. Thus, hydrophobic interaction of hydrocar-
bon tail of surfactant(s) and alkanol become more pronounced, and
elongated tails of amphiphiles are gradually twisted to achieve
effective bonding with aid of van der Walls type of interactions.
In this way, dI of the droplets becomes smaller with increasing
water content [32].
With increasing water content, Nd values obviously decrease for
all these systems so as to satisfy the thermodynamic requirement
of stability under the condition of invariable surfactant content.
This type of variation was also reported by several authors using
single surfactants (similar or dissimilar with present report) de-
rived microemulsions [30,32,33,37].
Both N s and N a values are increased with increasing x, which
indicates growing surface area of the droplets. The increased pro-
107
40
A Hp B
Dc
30
20
10
0
60 80 100
-80 -60 -40 -20 0 20 40 60 80 100 120
-10
R2 = 0.9997
-20
Tcomp = 300.6K
-30
Δ S 0t (J K-1 mol-1)
portion of N a on the droplet surface (or N a =N s values are greater
than unity) meant an effective stabilizing role of Pn toward the for-
mation of dispersion [37]. Similar results were also reported in lit-
erature [30,32,33,37]. It reveals from Fig. S6(A) that N a =N s values
gradually increase with x up to a certain value (i.e., x = 30) for
both oils and thereafter a gradual decrease in N a =N s values. Similar
trend is observed for nia =ns vs. x and subsequently discussed in the
preceding Section 3.1.1. Paul et al. [32] reported similar transition
for CPC/Pn/Dc or Dd/water systems at comparable physicochemi-
cal environments. Hence, validity of structural parameters evalu-
ated from theoretical models is justified from the plots of nia =ns
vs. x and N a =N s vs. x.
3.3.2. Effect of chain length of oil and nonionic surfactant
It reveals from Table 3 that Re and Rw values are lower for Dc
stabilized systems than Hp and also for CPC/Brij-78 stabilized sys-
tems than CPC/Brij-58 stabilized systems under comparable condi-
tions. It is quite likely that large numbers of Pn molecules are
required to form a stable w/o microemulsion at a particular x
for Dc than Hp and also for CPC/Brij-78 system than CPC/Brij-58
system (Table 1), and hence, the interface becomes more flexible.
Thereby, splitting of larger droplets into smaller one, which in turn
produces larger surface area, only satisfies the accommodation of
excess Pn at the interface [32]. It was reported that with increasing
the amount of alcohol in the interface, diminishing the droplet ra-
dius for CPC/Pn/Dc (or, Dd)/water [32], SDS + Brij-58 (or, Brij-78)/
Pn/Hp (or, Dc)/water [40], and SDS/Pn (or Hx)/Dd/water micro-
emulsions [81].
With the increase in chain length from Hp to Dc, dI values
mildly increase at the studied x range, keeping other parameters
constant. It is quite likely that dI of (CPC + Brij-78, with steryl
hydrocarbon chain) stabilized system is mildly larger than
(CPC + Brij-58, with cetyl hydrocarbon chain) system, as dI consti-
tutes hydrocarbon tails of the surfactants [82]. It is suggested that
the transition from w/o to o/w microemulsion system is expected
to attain at higher water content when Hp is replaced by Dc and
Brij-58 is replaced by Brij-78. Alternatively, the maximum solubi-
lization capacity is increased from Hp to Dc and Brij-58 to
 108 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110

Brij-78. Hence, an indirect estimation of the maximum solubiliza-

Structural parameters of the w/o microemulsion at a constant amount of surfactant (0.5 mmol) with fixed temperature (303 K) and composition (XBrij58 or Brij 78 = 0.2) at different x. System: CPC/Brij-58 or Brij-78/Pn/Hp(or, Dc)/water.

[3.97(4.40)]
[2.86(3.20)]

[1.38(3.04)]
[3.34(3.80)]

[3.72(4.05)]
tion capacity may be interpreted from the above results.

2.79(3.77)

2.32(2.72)
1.67(2.70)

0.49(1.54)
1.90(3.00) In Fig. S6(B), Nd vs. x profile at 303 K shows more efficient dis-
N a =N s

persion of water in CPC/Brij-78 systems than in CPC/Brij-58 sys-

tems; formation of a bigger interface with a large number of
lower dimension water droplets are envisaged. Similar observa-
tion was reported by Mitra et al. [36] for C2 or C3/Hx/i-Oc/water
system. On the other hand, Dc stabilized systems exhibit higher
Nd values than Hp. These observations are substantiated from
N a (per droplet)

low Re values [Table 3].

N a values are found to be larger for CPC/Brij-78 system than
[685(711)]
[319(342)]

[485(516)]

[665(982)]
[848(870)]
346(454)

585(666)

694(745)
215(303)

305(706)

CPC/Brij-58 system in both oils. Similar trend in N a values is ob-

served for Dc derived systems compared to Hp derived systems
in all cases. These two observations are well substantiated from
nia values, which have been dealt earlier (Section 3.1.1 and Table 1).

4. Conclusions
N s (per droplet)

The main findings of the work reported here are summarized

[173(162)]
[145(136)]

[228(215)]

[483(324)]
[111(107)]

below:
129(112)

182(151)

299(274)

617(459)
209(176)

The interfacial and bulk compositions as well as the distribu-

tion of Pn between the interface and bulk oil (obtained by the
Schulman cosurfactant titration of the oil/water interface) depend
on the interaction between the surfactant(s) at the interface, vis-
a-vis their compositions, hydrocarbon chain length of nonionic
surfactant and oil, and thermal condition. These parameters
played a role to govern the lipase activity on membrane mimetic
Nd  1018 (per droplet)

system under varied x and molar ratio of cosurfactant and surfac-

tant ðnia =nsÞ [19]. DG0t for transfer process (Pnoil ? Pnint) is sponta-
neous for (CPC + Brij-58 or Brij-78)/Pn/Hp (or, Dc)/water systems,
but the degree of spontaneity depends on x, XBrij-58 or Brij-78, chain
[1.75(1.86)]
[2.70(2.82)]

[2.07(2.22)]

[1.32(1.40)]

[0.62(0.93)]
2.34(2.69)

1.66(1.99)

1.44(1.71)

1.01(1.10)

0.49(0.66)

length of nonionic surfactant (Brij-58 or Brij-78) and oil (Hp or Dc)

and temperature. The transfer process of Pn (Pnoil ? Pnint) favors
at high temperatures and all compositions in both oils, except at
lower mole fraction of Brij-78 (i.e., XBrij-78 6 0.4). DG0t values
may be useful for predicting the size of the nanoparticles synthe-
sized in these mixed surfactant w/o microemulsions in accor-
dance with the report made by He et al. [83] and Zhu et al. [84]
for the synthesis of cerium oxalate, Ce2(C2O4)310H2O and samar-
[1.31(1.33)]
[1.51(1.53)]

[1.37(1.39)]

[1.24(1.25)]

[1.09(1.17)]
1.41(1.49)

1.27(1.34)

1.24(1.29)

1.16(1.18)

1.02(1.08)

ium oxide (Sm2O3) nanoparticles, respectively. The overall mixed

dI (nm)

surfactant-based microemulsion forming systems have been

ended up with absorption or release of heat and with ordered or
disordered state, depending on their chemical compositions (i.e.,
the constituent surfactant(s) with their configurations, content
and type of oil), and thermal condition. Enthalpy and entropy
changes well compensate each other. Temperature insensitive
microemulsions with zero ðDC 0p Þt have been formed at specific
[3.33(3.26)]
[1.99(1.97)]

[5.57(4.87)]
[2.75(2.69)]

[4.02(3.95)]
2.96(2.78)

3.55(3.36)

compositions for these mixed surfactant systems due to opposite

4.40(4.28)

6.07(5.47)
2.10(2.00)
Rw (nm)

behavior of ionic and nonionic surfactant toward temperature

[65,66]. Such types of microemulsion formulations have been
found to be useful in various commercial and technological pro-
cesses [73]. Structural parameters (both Re and Rw) increase with
increase in x (=10–50). The adjustable radius of the water pool
Values for CPC/Brij-78/Hp(Dc) systems.

provides a potential application to the synthesis of metal nano-

particles with different sizes using these w/o microemulsions as
Values for CPC/Brij-58/Hp(Dc).
[3.50(3.48)]b

[4.64(4.59)]
[4.11(4.08)]

[5.26(5.20)]

[6.66(6.04)]

templates [30–32]. These microemulsion systems may be used

a
3.51(3.49)

4.23(4.12)

4.79(4.64)

5.56(5.46)

7.09(6.56)

to study the activity of enzyme (CV-lipase, HRP [85] and HLADH

Re (nm)

[49]), as it was reported that nonionic surfactant and concentra-

tion of Pn not only influence the enzymatic activity, but also use-
ful complement for the investigation of microemulsion structures.
These mixed surfactant microemulsions could be a potential
template for synthesis of nanoparticles as particle growth rate,
final size, and polydispersity are affected by the addition of poly-
Table 3

oxyethylene alkyl ether type nonionic surfactants (viz. Brij-58 or

10

20

30

40

50
x

b
a

Brij-78) and cosurfactant (Pn), which influence the flexibility of

 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110 109

the interfacial film [86]. N a =N s values greater than unity signify an Kd Distribution constant of alkanol between
effective stabilizing role of Pn toward the formation of dispersion. interface and oil
Nd vs. x profiles at 303 K showed more efficient dispersion of water DG0t ; DH0t ; DS0t and Standard Gibbs free energy, enthalpy,
in CPC/Brij-78 systems than CPC/Brij-58 systems, for interface with entropy and specific heat capacity of
ðDC 0p Þt
a large number of lower dimension of water droplets are envisaged. transfer of alkanol from oil to the
The catalytic efficiency of lipase at the interface of CPC/Brij-78 sta- interface, respectively
bilized w/o microemulsions can be finely modulated due to large P and Peff Packing parameter and effective packing
interfacial area, which is a relevant variable for the enzyme activity parameter, respectively
[19]. Hence, the evaluation of all these parameters to underline the vc, ao and lc Hydrocarbon chain volume, optimum
modification of the oil/water interface by mixing the nonionic headgroup area per molecule and
surfactants (Brij-58 or Brij-78) and cosurfactant (Pn), which in turn hydrocarbon chain length of amphiphile,
affects the water solubilization capacity and states of the water respectively
inside the water pool, and is helpful to advance the development Re and Rw Radius of the droplet including the
of the colloid and interface science from both fundamental and interface and radius of the water pool,
application points of view. respectively
dI Thickness of the interfacial layer
Acknowledgments Nd Total number of droplets
N s and N a Average aggregation number of
The financial support in the form of an operating research grant surfactant and cosurfactant per droplet,
to B.K.P, Senior Research Fellowship to K.K., and project assistant- respectively
ship to G.G. from the authority of Indian Statistical Institute, Kolk- Vd Total volume of the dispersed droplets
ata, India, are thankfully acknowledged. We express our sincere per ml volume of solution
thanks to the reviewers for improvement of the manuscript. Ad Droplet surface area
V H2 O , Vs and V ia Volumes of water, surfactant and alkanol
at the interface, respectively
Appendix A. Abbreviations and nomenclature Ma and qa Molar mass and density of alkanol
Vtail and Vhead Volumes of tail and head per surfactant
molecule, respectively
NA Avogadro number
CPC Cetylpyridinium chloride nc Number of carbon atom in the
Brij-58 (C16E20) Polyoxyethylene (20) cetyl ether hydrophobic tail of the surfactant
Brij-78 (C18E20) Polyoxyethylene (20) stearyl ether As and Aa Area of the polar head group of the
C12-s-C122Br, Alkanediyl-a,x-bis-(dimethyldodecyl- surfactant and alkanol, respectively
where s = 2–6 ammonium bromide) V hs and V ha Volumes of the surfactant and alkanol
C12-EOx-C122Br, (Oligooxa)alkanediyl-a,x-bis- headgroups
where x = 1–3 (dimethylalkyl-ammonium bromide) (As)mix, (Vs)mix and Area of the polar head group, total
CnTAB, where Alkyltrimethylammonium bromide ðV hs Þmix volume and head group volume of
n = 10, 14, 16 surfactant mixtures, respectively
PS 40, PS 60 and PS Polyoxyethylene (20) sorbitan Xs1 and Xs2 Mole fraction of surfactant 1 and
80 monopalmitate, polyoxyethylene (20) surfactant 2, respectively
sorbitan monostearate and As1 and As2 Polar head group area of surfactant 1 and
polyoxyethylene (20) sorbitan surfactant 2, respectively
monooleate, respectively
C2 N-hexadecyl-N,N-bis(2-
hydroxyethyl)ammonium bromide
C3 N-hexadecyl-N,N,N-tris(2-
hydroxyethyl)ammonium bromide Appendix B. Supplementary material
XBrij-58 or Brij-78 mole fraction of Brij-58 or Brij-78 in
(CPC + Brij-58 or Brij-78) mixtures Supplementary data associated with this article can be found, in
Bu, Pn, Hx, Hp, Dc, Butanol, pentanol, hexanol, heptane, the online version, at http://dx.doi.org/10.1016/j.jcis.2012.06.057.
Dd and i-Oc decane, dodecane and isooctane,
respectively References
w/o Water-in-oil
[1] S.P. Moulik, B.K. Paul, Adv. Colloid Interface Sci. 78 (1998) 99.
x Water-to-surfactant mole ratio [2] T.K. De, A. Maitra, Adv. Colloid Interface Sci. 59 (1995) 95.
HRP Horseradish peroxidase [3] M. Wang, J.K. Thomas, T. Nowak, J. Am. Chem. Soc. 99 (1977) 4730.
HLADH Horse liver alcohol dehydrogenase [4] N.E. Levinger, L.A. Swafford, Ann. Rev. Phys. Chem. 60 (2009) 385.
[5] B.K. Paul, R.K. Mitra, J. Colloid Interface Sci. 288 (2005) 261.
nia ; nw o
a and na
Number of moles of alkanol in the [6] L.M.M. Nazario, T.A. Hatton, J.P.S.G. Crespo, Langmuir 12 (1996) 6326.
interface, water and oil phases, [7] A. Bumajdad, J. Eastoe, Phys. Chem. Chem. Phys. 6 (2004) 1597.
respectively [8] T. Kinugasa, A. Kondo, S. Nishimura, Y. Miyauchi, Y. Nishii, K. Watanabe, H.
Takeuchi, Colloids Surf., A 202 (2004) 193.
ns, na and no Total number of moles of surfactant, [9] A. Bumajdad, J. Eastoe, R.K. Heenan, R.J. Lu, D.C. Steytler, S.E. Egelhaat, J. Chem.
alkanol and oil, respectively Soc., Faraday Trans. 94 (1998) 2143.
nia =ns Compositional variations of amphiphiles [10] A. Bumajdad, J. Eastoe, P. Griffiths, D.C. Steytler, R.K. Heenan, J.R. Lu, P.
Timmins, Langmuir 15 (1999) 5271.
(both surfactants and cosurfactant) at [11] A. Bumajdad, J. Eastoe, S. Nave, D.C. Steytler, R.K. Heenan, I. Grillo, Langmuir 19
the interface (2003) 2560.
110 K. Kundu et al. / Journal of Colloid and Interface Science 385 (2012) 96–110
[12] Q. Li, T. Li, J. Wu, J. Phys. Chem. B 104 (2000) 9011.
[13] W. Zhang, X. Qiao, J. Chen, Q. Chen, Matter. Lett. 62 (2008) 1689.
[14] R. Najjar, C. Stubenrauch, J. Colloid Interface Sci. 331 (2009) 214.
[15] M. Magno, D.G. Angelescu, C. Stubenrauch, Colloids Surf., A 348 (2009) 116.
and references therein.
[16] N.L. Abbott, R.A. Maykay, Curr. Opin. Colloid Interface Sci. 4 (1999) 323.
[17] N. Garti, Curr. Opin. Colloid Interface Sci. 8 (2003) 197.
[18] W. Kunz, D. Touraud, P. Baudin, in: M. Fanun (Ed.), Microemulsions: Properties
and Applications, CRC Press (Taylor and Francis Group), USA, 2009, p. 331.
[19] F. Lopez, G. Cinelli, L. Ambrosome, A. Clafemmina, A. Ceglie, G. Palazzo, Colloids
Surf., A 237 (2004) 49.
[20] S.R. Bisal, P.K. Bhattacharya, S.P. Moulik, J. Phys. Chem. 94 (1990) 350.
[21] R.K. Mitra, S.S. Sinha, P.K. Verma, S.K. Pal, J. Phys. Chem. B 112 (2008) 12946.
[22] J.E. Bowcott, J.H. Schulman, Z. Electrochem 59 (1955) 283.
[23] K.S. Birdi, Colloid Polym. Sci. 260 (1982) 628.
[24] S. Kumar, S. Singh, H.N. Singh, J. Surf. Sci. Technol. 2 (1986) 85.
[25] H.N. Singh, C.D. Prasad, S. Kumar, J. Am. Oil Chem. Soc. 70 (1993) 69.
[26] L. Digout, K. Bren, R. Palepu, S.P. Moulik, Colloid Polym. Sci. 279 (2001) 655.
[27] S.K. Hait, S.P. Moulik, Langmuir 18 (2002) 6736.
[28] M. Giustini, S. Murgia, G. Palazzo, Langmuir 20 (2004) 7381.
[29] M.M. Moohareb, R.M. Palepu, S.P. Moulik, J. Dispersion Sci. Technol. 27 (2006)
1209.
[30] O. Zheng, J-Xi. Zhao, X-Ming. Fu, Langmuir 22 (2006) 3528.
[31] O. Zheng, J-Xi Zhao, H. Yan, S-Kang Gao, J. Colloid Interface Sci. 310 (2007) 331.
[32] B.K. Paul, D. Nandy, J. Colloid Interface Sci. 316 (2007) 751.
[33] M. De, S.C. Bhattacharya, A.K. Panda, S.P. Moulik, J. Dispersion Sci. Technol. 30
(2009) 1262.
[34] M. De, S.C. Bhattacharya, S.P. Moulik, A.K. Panda, J. Surfactants Deterg. 13
(2010) 475.
[35] S.K. Mehta, G. Kaur, R. Mutneja, K.K. Bhasin, J. Colloid Interface Sci. 338 (2009)
542.
[36] D. Mitra, I. Chakraborty, S.C. Bhattacharya, S.P. Moulik, S. Roy, D. Das, P.K. Das,
J. Phys. Chem. B 110 (2006) 11314.
[37] K. Maiti, I. Chakraborty, S.C. Bhattacharya, A.K. Panda, S.P. Moulik, J. Phys.
Chem. B 111 (2007) 14175.
[38] R.K. Mitra, B.K. Paul, S.P. Moulik, J. Colloid Interface Sci. 300 (2006) 755.
[39] J.L. Chai, Y. Li, X.N. Xue, J.J. Lu, Z.M. Zhang, J. Dispersion Sci. Technol. 31 (2010)
1050.
[40] K. Kundu, B.K. Paul, communicated.
[41] G. Gu, W. Wang, H. Yen, J. Therm. Anal. 51 (1998) 115.
[42] S.P. Moulik, L.G. Digout, W.M. Aylward, R. Palepu, Langmuir 16 (2000) 3101.
[43] R.L. Venable, J. Am. Oil Chem. Soc. 62 (1985) 128.
[44] P.M. Holland, D.N. Rubing (Eds.), Cationic Surfactants: Physical Chemistry,
Marcel Dekker, New York, 1991.
[45] J.M. Richmond (Ed.), Cationic Surfactants: Organic Chemistry, Marcel Dekker,
New York, 1990.
[46] R.P. Bagwe, K.C. Khilar, Langmuir 16 (2000) 905.
[47] M. Andersson, J.S. Pedersen, A.E.C. Palmqvist, Langmuir 21 (2005) 11387.
[48] A. Bumajdad, J. Eastoe, M.I. Zaki, R.K. Heenan, L. Pasupulety, J. Colloid Interface
Sci. 312 (2007) 68.
[49] A. Meziani, D. Touraud, A. Zradba, S. Pulvin, I. Pezron, M. Clausse, W. Kunz, J.
Phys. Chem. B 101 (1997) 3620.
[50] S. Bardhan, B.K. Paul, S. Saha, communicated.
[51] S. Ghosh, J. Colloid Interface Sci. 244 (2001) 128.
[52] R.A. Horne, J.P. Almeida, A.F. Day, N.-T. Yu, J. Colloid Interface Sci. 35 (1971) 77.
[53] K. Tasaki, J. Am. Chem. Soc. 118 (1996) 8459.
[54] K.L. Mittal, D.O. Shah (Eds.), Adsorption and Aggregation of Surfactants in
Solutions, CRC Press (Taylor and Francis Group), NY, 2005.
[55] J.N. Israelachvili, D.J. Mitchell, B.W. Ninham, J. Chem. Soc., Faraday Trans. 172
(1976) 1525.
[56] C. Tanford, J. Phys. Chem. 76 (1972) 3020.
[57] G.G. Warr, R. Sen, D.F. Evans, J.E. Trend, J. Phys. Chem. 92 (1988) 774.
[58] A. Dupont, J. Eastoe, M. Murray, L. Martin, F. Guittard, E.T. De Givenchy,
Langmuir 20 (2004) 9953.
[59] H. Preu, A. Zrabda, S. Rost, W. Kunz, E.H. Hardy, M.D. Zeidler, Phys. Chem.
Chem. Phys. 1 (1999) 3321.
[60] J. Schefer, R. McDaniel, B.P. Schoenborn, J. Phys. Chem. 92 (1988) 729.
[61] J. Lang, G. Mascolo, R. Zana, P.L. Luisi, J. Phys. Chem. 94 (1990) 3069.
[62] D.F. Evans, B.W. Ninham, J. Phys. Chem. 90 (1986) 226.
[63] M.J. Hou, M. Kim, D.O. Shah, J. Colloid Interface Sci. 123 (1988) 398.
[64] R. Leung, D.O. Shah, J. Colloid Interface Sci. 120 (320) (1987) 330.
[65] K.V. Schubert, G. Busse, R. Strey, M. Kahlweit, J. Phys. Chem. 97 (1993) 248.
[66] B.P. Binks, P.D.I. Fletcher, D.J.F. Taylor, Langmuir 13 (1997) 7030;
B.P. Binks, P.D.I. Fletcher, D.J.F. Taylor, Langmuir 14 (1998) 5324.
[67] S. Ghosh, A.D. Burman, G.C. De, A.R. Das, J. Phys. Chem. B 115 (2012) 11098.
[68] O. Owoyomi, J. Ige, O.O. Soriyan, Chem. Sci. J. (2011) CSJ-25.
[69] K. Khougaz, Z. Gao, A. Eisenberg, Langmuir 13 (1997) 623.
[70] S. Ray, S.P. Moulik, J. Colloid Interface Sci. 173 (1995) 28.
[71] G.B. Ray, I. Chakraborty, S. Ghosh, S.P. Moulik, J. Colloid Interface Sci. 307
(2007) 543.
[72] S.K. Mehta, S. Chadhary, K.K. Bhasin, J. Colloid Interface Sci. 321 (2008) 426.
[73] P. Bauduin, D. Touraud, W. Kunz, Langmuir 21 (2005) 8138.
[74] R. Lumry, S. Rajender, Biopolymers 9 (1970) 1125.
[75] D.M. Zhu, K.I. Feng, Z.A. Schelly, J. Phys. Chem. 96 (1992) 2382.
[76] L.-J. Chen, S.-Y. Lin, C.-C. Huang, J. Phys. Chem. B 102 (1998) 4350.
[77] R. Nagarajan, E. Ruckenstein, Langmuir 16 (2000) 6400.
[78] S.P. Moulik, M.L. Das, P.K. Bhattacharya, A.R. Das, Langmuir 8 (1992) 2135.
[79] S. De, V.K. Aswal, P.S. Goyal, S. Bhattacharya, J. Phys. Chem. B 102 (1998) 6152.
[72] S.K. Mehta, S. Chadhary, K.K. Bhasin, J. Colloid Interface Sci. 321 (2008) 426.
[81] J. Biais, J.F. Bodet, B. Clin, P. Lalanne, D. Roux, J. Phys. Chem. 90 (1986) 5835.
[82] W.-X. Shi, H.-X. Guo, J. Phys. Chem. B 114 (2010) 6365.
[83] Y. He, B. Yang, G. Cheng, H. Pan, Mater. Lett. 58 (2004) 2019.
[84] W. Zhu, L. Xu, J. Ma, R. Yang, Y. Chen, J. Colloid Interface Sci. 340 (2009) 119.
[85] A. Shome, S. Roy, P. Das, Langmuir 23 (2007) 4130.
[86] J. Eastoe, M.J. Hollamby, L. Hudson, Adv. Colloid Interface Sci. 128–136 (2006)
5.