Chemical Engineering Science 102 (2013) 176–185

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Stability of oil-in-water macro-emulsion with anionic surfactant: Effect

of electrolytes and temperature
Partha Kundu, Akanksha Agrawal, Haaris Mateen, Indra M. Mishra n
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Roorkee, 247667, Uttarakhand, India

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Effect of electrolytes on the stability Schematic representation of phase inversion temperature (PIT) of oil–anionic surfactant–water emulsion
of o/w emulsion with SDBS was with different surfactant to oil (s/o) ratio (w/w): 0.1 (―
―); 0.2 (―○―); 0.3 (―▼―); 0.4 (―Δ―); 0.5 (―■―); 0.6
investigated. (―□―); and 0.7 (―♦―).

PIT of o/w emulsion with SDBS was
studied by electrical conductivity.

As the valency of cations increases,
PIT increases; the reverse is true for
anions.

Turbidity measurements show a
decrease in the rate of de-
emulsification with time.

The destabilization of emulsion was
governed by coalescence and Ost-
wald ripening.

art ic l e i nf o a b s t r a c t

Article history: This paper reports on the destabilization of oil-in-water macro-emulsions prepared with diesel oil
Received 20 May 2013 dispersed in a continuous water phase and stabilized by an anionic surfactant—sodium dodecyl benzene
Received in revised form sulphonate (SDBS). Phase inversion temperature (PIT) of anionic surfactant–oil–water emulsion system
21 July 2013
was determined by measuring the conductivity as a function of temperature at different surfactant to oil
Accepted 31 July 2013
ratios. The influence of different kinds of inorganic salts on the PIT, electrophoretic properties and long-
Available online 11 August 2013
term stability of the o/w emulsion were studied by making measurements of conductivity, zeta potential
Keywords: and turbidity of the emulsion. PIT was found to be a linear function of logarithmic molar concentration of
Oil-in-water (o/w) emulsions the electrolytes. Droplet size distribution of stable emulsion is found to have broader range for mono-
Anionic surfactant
valent electrolytes than that of higher valence cations. Larger the valence of cations, lower is the stability
PIT
of the emulsion. By analyzing the evolution of emulsion droplet size, and turbidity of the resulting
Coalescence
Ostwald ripening emulsion with time, the main destabilizing mechanisms of the o/w macro-emulsion were explained. It is
Zeta potential found that coalescence, and Ostwald ripening could be the main destabilizing mechanisms of o/w macro-
emulsion.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction emulsions are thermodynamically unstable and are provided with

An emulsion is a colloidal dispersion of two immiscible liquid
phases, with one liquid phase present as small spherical droplets
(a dispersed phase) in the other (a continuous phase). The
n
Corresponding author. Tel.: +91 11332 285715; fax: +91 1332 276535.
E-mail addresses: immishra49@gmail.com, immishfch@iitr.ac.in (I.M. Mishra).
kinetic stability by an adsorbed layer of surface-active material,
e.g. surfactant molecules (Dickinson, 1992). Since the total surface
energy of the system is lowered by the coalescence of emulsion
droplets, the stability of an emulsion system, therefore, depends
on the rate of coalescence. The rate of coalescence depends on the
height of the potential energy barrier preventing the tendency of
approach of two emulsion droplets towards each other. If the
barrier is much higher than thermal energy, the rate of coalescence is

0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.07.050
 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185
practically zero and the emulsion becomes stable. The potential
energy barrier for charged oil droplets in water arises from the
electrostatic interactions between the droplets. The stability of
charged colloidal and emulsion particles in water can be explained
by DLVO theory. According to this theory, the barrier height is
determined by the van der Waals force and the electrostatic force.
The electrostatic force is the sum of Maxwell's electric fields stress
and the osmotic pressure. The van der Waals force and Maxwell's
stress are always attractive, whereas the osmotic pressure is usually
repulsive (Verway and Overbeek, 1948). This theory is based on the
assumptions that the surface potentials of emulsion droplets are
uniform and the same for all the droplets, as long as the separation
distances between the droplets are much larger than the thickness of
the diffuse electrical double layers around the droplets. When two
droplets approach and come closer to each other and the distance
between them is less than the thickness of the electrical double layer,
electrostatic interaction occurs between the two surfaces, resulting in
a change of the surface potentials. The surface ions adsorbed on the
droplets then migrate to compensate for the induced potential
change. If the surface charges move freely like conduction electrons
on metallic spheres, the migration of the surface charges completely
compensates the potential gradient on the surfaces. If the migration
of surface charges is completely prohibited, the surface potentials
continuously increase with a decrease in separation distance, and
become infinite at zero separation distance. The actual situation for
oil-in-water (o/w) or water-in-oil (w/o) emulsion droplets may lie
somewhere between these two extreme cases (Ichikawa et al., 2006).
Macro-emulsion composed of drops in the micrometer-size
range is not thermodynamically stable. Because of various sources
of instability present in the system, phase separation occurs
eventually. Emulsion type and stability are known to be associated
with the equilibrium phase behaviour in surfactant-oil-water
systems and also with the hydrophile–lipophile balance (HLB) of
the system (as opposed to the empirical HLB number of the
surfactant), which is related to the locus of aggregate formation
in equilibrated mixtures (Binks, 1999; Binks et al., 2000). Macro-
emulsions do not form spontaneously but rather require an input
of energy. The common mechanisms leading to physical instability
of o/w macro-emulsions include creaming or sedimentation,
flocculation, and coalescence (Palanuwech and Coupland, 2003).
Creaming or sedimentation of drops can occur depending on the
density difference between the dispersed and continuous phases
and can be enhanced or restricted by flocculation (Binks, 1999).
Here, the original droplet size distribution of the emulsion is not
altered during separation. A seemingly straightforward extension
of creaming or sedimentation is flocculation where the droplets
associate with each other forming weakly bound flocks of larger
average size, thereby allowing gravitational influence to dominate
the system.
For coalescence phenomenon to take place, the thinning of
film between approaching drops must reach a critical thickness.
It has been proposed that when two large drops of millimetre
size approach each other, they deform and a planar film forms
between them (Ivanov, 1980). The rate of thinning and the
stability against rupture of this film determines the overall
stability to coalescence of the emulsion. Another destabilization
mechanism is the Ostwald ripening, but this phenomenon
basically occurs for emulsions with very fine droplets, in the
nanometre size range i.e. nano-emulsions. Ostwald ripening is
the growth of large drops at the expense of smaller ones and
relies on the transport and solubility of the dispersed phase in
the continuous phase. Oil-in-water emulsions are stabilized
mainly by electrostatic interactions and the adsorption of
macromolecules or solid particles at the oil–water interface.
The ionic strength of the continuous phase has a strong
influence on the zeta potential of the oil droplets, and this
177
parameter controls the electrostatic interactions, thereby influ-
encing the emulsion stability (Ríos et al., 1998).
A majority of publications discussed about the formation and
stability of w/o nano-emulsions with non-ionic surfactants.
Shinoda and Saito (1969, 1970) investigated the effect of salt
addition and temperature on the phase diagram and hydrophile–
lipophile balance (HLB) of water–cyclohexane system stabilized
with non-ionic surfactant (polyoxy-ethylene-nonylphenylether).
Uson et al. (2004) studied the phase behaviour of water–
non-ionic surfactant–oil system. Porrasa et al. (2004) studied the
formation of w/o nano emulsion with mixed non-ionic surfactants
along with emulsion breakdown mechanisms. Liu et al. (2006)
studied the formation and stability of paraffinic o/w nano-
emulsion stabilized with non-ionic surfactant (Tween 80/Span
80). Recently, a few studies reported on the effect of inorganic
salts on the stability of o/w nano-emulsion with non-ionic
surfactants. They used NaCl, KCl, CaCl2, AlCl3 and Na2SO4. They
showed that the addition of salting out salts in water can reduce
the phase inversion temperature (PIT) of the systems to an
optimum temperature, exhibiting ease in the formation of nano-
emulsions. Mei et al. (2011) studied the influence of different types
of inorganic salts on the PIT and long-term stability of paraffin oil–
water nano-emulsions with non-ionic surfactants (Tween 80/Span
80). Sharif et al. (2012) investigated the effect of NaCl and Na2SO4
concentration on the PIT of n-hexadecane–non-ionic surfactant
(C12E14)–water system. Jiang et al. (2013) studied the effect of
inorganic salts such as NaCl, CaCl2 and Na2SO4 on the formation of
water-in-oil (w/o) emulsion (not o/w emulsion) and its stability.
They used a paraffinic oil and polyoxyethylene 4 lauryl ether (Brij
30) as a non-ionic hydrophilic surfactant in water to form w/o
emulsion. They reported an increase in the stability with an
increase in the salt concentration and found that the formation
of nano w/o emulsion by the PIT method is difficult if it is
stabilized at room temperature. Information about the stability
of o/w macroemulsion stabilized with anionic surfactant is very
limited. In this context, we have investigated the effect of various
electrolytes and temperature on the stability of oil–anionic surfac-
tant–water system. Moreover, the oil droplet distribution was
observed systematically to evaluate the growth rate of the droplets
and to figure out the possible emulsion instability mechanism.
In the present work, oil-in-water emulsions were prepared
with diesel oil, and an anionic surfactant sodium dodecyl benzene
sulphonate (SDBS)—was used along with water. The effect of
various electrolytes, such as NaCl, Na2SO4, KCl, CaCl2 and AlCl3
on PIT, electrophoretic properties and long-term stability was
studied. Droplet size distribution was measured for different
surfactant to oil (s/o) ratios and electrolyte concentrations by a
particle size analyser (CIS 100). The effects of electrolyte concen-
tration and ionic charge on zeta potential of o/w emulsion have
also been reported. The turbidity of o/w emulsions with different
electrolyte concentrations was measured to monitor the perfor-
mance of the demulsification process. The mechanism of instabil-
ity of oil–anionic surfactant–water emulsion system was also
studied.
2. Experimental
2.1. Materials
Diesel oil (density, ρ ¼830 kg/m3, viscosity, m ¼2.0–4.5 cSt)
(Indian Oil Corporation Ltd., India), sodium dodecyl benzene
sulphonate (SDBS) (Himedia, Mumbai), NaOH (RFCL, New Delhi),
anhydrate Na2SO4 (Rankem, New Delhi), NaCl (SRL, Mumbai), KCl
(SRL, Mumbai), anhydrate AlCl3 (Rankem, New Delhi), CaCl2
(Rankem, New Delhi), Na2CO3 (NICE, Cochin) were used in the
178 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185

Table 1
Physico-chemical properties of sodium dodecyl benzene sulphonate (SDBS).

Characteristics

Type Anionic surfactant

Molecular formula CH3(CH2)11C6H4SO3Na
Molecular weight 348.48
Structural formula

Appearance White or pale yellow powder

Apparent density (g/ml) 0.18
Minimum assay (%) 20.0
Moisture content (%) 5.0

Table 2
Details of SDS and SDBS (Anionic surfactant).

Surfactant Sodium dodecyl sulphate (SDS) sodium dodecyl benzene sulphonate (SDBS)

Chemical formula C12H25O4SNa CH3(CH2)11C6H4SO3Na

Structure

Molecular weight (MW) 288.38 348.48

Critical micelle concentration 8.3  10  3 mM 1.20  10  3 mM
(CMC) in water
Equilibrium partition constant 17.9 dm3/mol 29.3 dm3/mol
(Kp)

experiments. SDBS was used as a surfactant and its physico-
chemical properties are shown in Table 1. All the reagents were
used as procured. Double distilled water was used for the
preparation of all o/w emulsions.
2.1.1. Selection of surfactant
Both SDS (C12H25NaO4S) and SDBS (C18H29NaO3S) are commer-
cially available anionic surfactants with a number of alkyl groups
(Table 2). However, SDBS has a larger number of hydrophobic side
chain group (–CH2–), which increases the hydrophobicity of SDBS
as compared to that of SDS, as also the number of binding sites
with hydrophobic part of o/w emulsion. The equilibrium partition
constant (Kp) of SDBS is higher than that of SDS, which signifies
that the hydrophobicity of SDBS is higher than that of SDS (Sarma
et al., 2005). Therefore, long hydrocarbon (hydrophobic) tail of
SDBS molecule penetrates more into the non-polar (oil) region of
o/w interface and gets attached electro-statically to a larger
number of oil droplets. That is why SDBS instead of SDS was
selected as a surfactant in the present study.
2.2. Methods
2.2.1. Preparation of o/w emulsion
The o/w emulsion was prepared synthetically by mixing diesel
oil, distilled water, sodium hydroxide, sodium chloride and SDBS
and stirring at 2000 revolutions per minute (rpm) using a
laboratory stirrer (Remi lab stirrer) for 10 min. For experiments
carried out to study the effect of NaCl or the chloride ions, the NaCl
concentration was varied in the range of 0.1–5.0 (M). Similarly, for
the effect of SDBS concentration, the surfactant to oil ratio
(weight/weight, w/w) was varied in the range of 0.1–0.7. All o/w
emulsions were, however, prepared with a fixed oil concentration
— 30% (v/v) or 24.9% (w/w). In order to observe the effect of
surfactant on thermal property as well as the stability of o/w
emulsion, surfactant concentration was varied from 25 g/dm3 to
175 g/dm3.The stability of emulsion was characterized by the
relative volume of emulsion constituents, defined as the ratio of
oil–water emulsion volume after 24 h of its preparation to the total
volume of water, oil and surfactant used together to prepare the
emulsion. The higher the ratio, the greater is the emulsion
stability.
2.2.2. Determination of phase inversion temperature (PIT)
The phase inversion temperature (PIT) of o/w macro-emulsion
was determined by using the electrical conductivity method.
Appropriate amount of anionic surfactant (SDBS), in different s/o
ratios, was added to o/w mixture containing 0.01 (M) NaCl solu-
tion at room temperature (  25 1C) and mixed by a high speed
laboratory stirrer. A sample of this stable o/w emulsion was then
heated gradually in a water bath and the conductivity and
temperature of the emulsion were simultaneously measured by a
conductivity meter (CON – 510, Oakton Instruments, USA). At the
beginning of the PIT test, where the conductivity changes rapidly,
the conductivity of o/w emulsion was measured with temperature
at every 1 min time interval. Thereafter, the conductivity changes
moderately and the measurements were made at every 2 min time
interval. After reaching PIT, the change in conductivity occurs
slowly. The conductivity meter had a cell constant of electrode,
K ¼1.0 and was equipped with a built-in temperature sensor for
automatic temperature compensation (ATC). The PIT of o/w emul-
sions was taken as the temperature at which the conductivity of
the resulting emulsion reaches a maxima and then decreases
sharply, exhibiting a phase inversion from o/w to w/o emulsion
and thereafter phase separation.
 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185
2.2.3. Determination of droplet size and stability
The droplet size distribution of the o/w emulsion was obtained
by using a particle size analyser (Ankersmid, CIS 100, Israel) at
25 1C. The long-term stability of o/w emulsions was assessed by
measuring the droplet size as a function of time. The samples were
kept sealed at room temperature (  25 1C). All droplet size
measurements were made twice and the average size is reported.
2.2.4. Turbidity measurements
The time dependence of dispersed droplets was measured by
monitoring the change in the turbidity of o/w emulsion. The
turbidity of o/w emulsion was determined by a turbidity meter
(Aqualytic, Germany).
2.2.5. Zeta potential measurement
The zeta potential of the o/w emulsion was measured by using
a zeta sizer (Malvern Nano ZS90) having a disposable folded
capillary cell made of polystyrene. The capillary cell was filled
with the o/w emulsion and then placed inside the instrument for
measuring the zeta potential at a temperature of 25 1C. This
apparatus includes a microprocessor that first measures the
electrophoretic mobility of colloidal particles dispersed in aqueous
solutions, and then automatically calculates the zeta potential
using the Smoluchowski equation.
3. Results and discussion
3.1. Phase inversion temperature of oil–anionic surfactant–water
emulsion
A series of o/w emulsions with varying surfactant to oil ratio
(0.1 r(s/o) r0.7 (w/w)) were prepared by mixing diesel oil–
water–surfactant (SDBS) with 0.01 (M) NaCl aqueous solution
and other chemicals as stated in Section 2.2.1. The type of
surfactant and its concentration play a vital role in the stability
of the o/w emulsions as well as in the droplet size distribution.
As the surfactant concentration increases from 25 g/dm3 to
175 g/dm3, the droplet size is reduced, causing an increase in the
ratio of surfactant film thickness to droplet radius (Tadros et al.,
2004). The relatively thicker surfactant film can provide better
steric stabilization against various instability processes, and make
the emulsion more stable.
The conductivity of the o/w emulsions is plotted against
temperature in Fig. 1. Only a few data points are shown for the
Fig. 1. Conductivity as a function of temperature of o/w emulsions (30 vol% oil)
having 0.01 M NaCl. s/o ratio (w/w): 0.1 (―
―); 0.2 (―○―); 0.3 (―▼―); 0.4 (―Δ―); 0.5
(―■―); 0.6 (―□―); and 0.7 (―♦―).
179
clarity of Fig. 1. It is observed that as the temperature increases,
the conductivity of o/w emulsion increases gradually, reaching a
maxima and thereafter, the conductivity decreases sharply and,
ultimately to zero at some temperature. The temperature, at which
the conductivity of o/w emulsion attains a maxima and thereafter
starts decreasing, is called the phase inversion temperature (PIT).
This occurs because of the phase splitting of the emulsion and
separation of the oil phase and water phase individually. At about
PIT, the change in conductivity occurs slowly. For oil-in-water
emulsion, water is the continuous phase which is conducting and
oil is the dispersed phase which is non-conducting. With an
increase in temperature, the viscosity of the emulsion gradually
decreases and demulsification process sets in. As temperature
increases, hydrogen bond and other forces (van der Waals forces)
which are acting at the interface become weaker. Therefore, water
molecules come out from the interface and coalesce together to
form water droplets. Hence, the conductivity of the emulsion
gradually increases. As the de-emulsification proceeds with an
increase in temperature, more and more water molecules diffuse
from the interface to the bulk phase, and after a certain period, the
volume fraction of the water phase becomes a maximum corre-
sponding to maximum conductivity of the emulsion. Due to
density difference, larger water molecules settle out from the
interface and the volume fraction of the aqueous phase gradually
decreases in the o/w emulsion system. This results in a decrease in
the conductivity at a temperature larger than PIT. Thereafter, the
conductivity of oil-water dispersion continuously decreases and
becomes negligible when complete phase separation takes place.
The PIT corresponds to the hydrophile–lipophile balance (HLB)
temperature of the emulsion system (Shinoda, 1968). The results
show a gradual decrease in the PIT from 60 1C to 30 1C with an
increase in s/o ratio from 0.1 to 0.7 (w/w). For o/w emulsions with
s/o ratio greater than 0.10, the conductivity of o/w emulsion
decreases after reaching the maximum. This phenomenon may
occur due to formation of liquid crystalline phase during the
transition from o/w emulsion to w/o emulsion (Kunieda et al.,
1996; Izquierdo et al., 2002; Morales et al., 2003). As the
temperature of the emulsion increases, the viscosity and the
interfacial tension between the oil micelle phase and the water
phase decrease with interfacial tension becoming zero when
complete phase separation takes place. During this temperature
change, liquid crystalline phase exists at the interface (Shinoda
and Saito, 1969). Hydrogen bonding plays an important role on the
structure of the liquid-crystalline phase (Winsor, 1968). As the
temperature increases, hydrogen bonding becomes weaker and
diminishes at elevated temperatures, when complete phase
separation occurs.
PIT of o/w emulsion varies with the type of oil and also the
hydrophilic chain length of the emulsifiers or surfactants. The
stability of o/w emulsion increases significantly with the chain
length of hydrophile–lipophile group of surfactant (Shinoda et al.,
1971). It may be assumed that the oligomers of polydispersed
surfactant show either synergism or competition for the interface,
depending on the number of polar and non-polar groups of each
oligomer (Crook et al., 1963; Somasundaran et al., 1991; Portet
et al., 1998). The interaction between hydrophilic portion and
water phase at the interphase strongly depends on temperature.
As the temperature of emulsion increases, the interaction between
hydrophilic group and the water phase becomes weaker (Shinoda
and Saito, 1969).
The PIT dependence on surfactant concentration may be
attributed to the poly-dispersity of the commercial surfactant
(Izquierdo et al., 2002). Poly-dispersity of a surfactant is mainly
concerned when dealing with the adsorption of the surfactant at
solid/liquid or liquid/liquid interfaces (Portet et al., 1998). The
dodecyl benzene sulphonate ion (DBS) of the anionic surfactant,
180 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185
Fig. 2. (a) Droplet size distribution of o/w emulsion with s/o ratio
(w/w) as a parameter at 25 1C. s/o ratio (w/w): 0.1 (―
―); 0.2 (―○―); 0.3 (―▼―);
0.4 (―Δ―); 0.5 (―■―); 0.6 (―□―); and 0.7 (―♦―). (b) Average diameter of oil droplets
as a function of s/o (w/w) ratio for o/w emulsion with 30 vol% diesel oil at 25 1C.
SDBS, has poly-dispersity, and is the main contributing factor to
the reduction of PIT. The poly-dispersity of SDBS arises due to the
wide distribution of alkyl chain and polar chain in the emulsion.
As the s/o ratio increases, the SDBS molecules with higher DBS ion
concentration get adsorbed onto the oil–water interface and the
molecules of lower DBS ion concentration move away from the
interface to the dispersed oil phase. As a consequence, the
surfactant layer curvature shifts from water phase to oil phase
and the slope of the curvature changes from positive to negative at
lower temperatures. Hence, the lowering of the PIT of the emul-
sion is observed.
3.2. Droplet size distribution
The droplet size distribution and the average droplet diameter
of o/w emulsions with different s/o ratios are presented in Fig. 2
(a) and (b). It is observed that with an increase in s/o ratio from
0.1 to 0.7 (w/w), the narrowing of droplet size distribution occurs,
and the initial average size of the droplets decreases from 26 μm
to 14 .μm. Usually the droplets of macro-emulsion are in the size
range of 1–50 mm. A number of researchers (Morales et al., 2003;
Liu et al., 2006; Mei et al., 2011) have reported the effect of
surfactant concentration on droplet size distribution and the
average droplet diameter in the emulsions.
The observed average size of droplets found in the present
study seems to be consistent with those reported by these
researchers. The surfactant concentration alters the interfacial
area and also the emulsion droplet size. Emulsions have a
tendency to reduce their interfacial area until they reach the
equilibrium stage. As the surfactant concentration increases, the
interfacial area between dispersed (oil) phase and continuous
(water) phase increases. This produces a large number of small
sized oil droplets with reduction in the growth rate of droplets,
leading to improved stability of emulsion (Shinoda, 1968; Schott
and Han, 1975, 1976; Haque et al., 1999; Peltonen and Yliruusi,
2000; Forgiarini et al., 2001; Morales et al., 2003; Capek, 2004).
The amount of surfactant is, thus, the most important parameter
in the formation of stable o/w emulsion, significantly influencing
the emulsion droplet number and size distributions. It is also
found that the o/w emulsion could not be formed when the s/o is
less than 0.1 (w/w). For further experiments, the o/w macro-
emulsions were prepared at a constant s/o ratio of 0.45 (w/w)
along with other inorganic salts, as discussed earlier.
3.3. Effect of inorganic salts on the PIT of o/w emulsions
3.3.1. Effect of anions
The effect of varying concentrations of NaCl and Na2SO4 on the PIT
of o/w emulsion was investigated by measuring the conductivity of
the emulsions at different temperatures. Figs. 3 and 4 show the
conductivity profile with temperature for NaCl and Na2SO4, respec-
tively. Lower the salt concentration, broader is the conductivity profile
with temperature. Both the figures indicate that the PIT increases
with a decrease in salt concentration, whereas the maximum
conductivity decreases with a decrease in salt concentration, as
expected. It is also observed that in the lower concentration range
(o0.05 M), NaCl concentration has little effect on the PIT of o/w
emulsion. This is consistent with the observation about electrolytes
(only a few data points are shown for clarity of the figure) exhibiting a
critical concentration above which their salting-in or salting-out effect
is observed (Goal, 1999). At a NaCl concentration greater than 0.05 M,
a larger reduction in PIT is observed (Fig. 3), mainly caused by the
salting-out effect of NaCl (Schott and Han, 1975, 1976; Iwanaga et al.,
1998). The salting-out effect influence the spontaneous curvature of
the surfactants at the oil–water interface.
Fig. 4 shows the effect of sulphate ions (SO42  ) on the PIT of
o/w emulsion. It is observed that at Na2SO4 concentrations less
than 0.05 M, the salt concentration has little effect on the PIT but
Fig. 3. Variation in the conductivity of o/w emulsion with temperature with NaCl
concentration as a parameter. NaCl concentration: 0.01 (M) (―
―); 0.05 (M) (―○―);
0.1 (M) (―▼―); 0.2 (M) (―Δ―); 0.5 (M) (―■―); 1 (M) (―□―); 2 (M) (―♦―); and 5
(M) (―◊―).
 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185
Fig. 4. Variation in the conductivity of o/w emulsion with temperature with
Na2SO4 concentration as a parameter. Na2SO4 concentration: 0.01 (M) (―
―); 0.02
(M) (―○―); 0.05 (M) (―▼―); 0.1 (M) (―Δ―); 0.2 (M) (―■―); and 0.5 (M) (―□―).
Fig. 5. PIT of o/w emulsion as a function of natural logarithm of molar concentra-
tions (C) of NaCl and Na2SO4. NaCl (―
―); Na2SO4 (―○―).
significant than that of chloride ions (Cl  ). The PIT of o/w emulsion
decreases sharply with an increase in Na2SO4 concentration
beyond 0.05 M. This decrease in PIT is also because of the
salting-out effect of Na2SO4 on the non-ionic surfactants, similar
to that observed for NaCl (Goal, 1999).
The salting-out effect of Na2SO4 is greater than that of NaCl at
the same molar concentration in consonance with the observa-
tions of Iwanaga et al. (1998) because of the Hofmeister series:
SO24  4Cl  . It is observed that at the same concentrations of the
two salts, o/w emulsions containing Na2SO4 have lower PIT than
that of NaCl containing emulsions. Hence, Na2SO4 reduces PIT for
o/w emulsion more strongly than the NaCl salt.
Fig. 5 shows a semi-logarithmic plot between PIT and the molar
concentration of the salts. It is found that the PIT can be
represented as a logarithmic function of molar concentration of
the electrolyte as follows:
PIT ¼ a lnC þ b
where a and b are constants, dependent on the electrolyte.
The values of ‘a’ and ‘b’ for NaCl and Na2SO4 (showing the effect
of Cl  and SO24  ions) are as follows:
NaCl: a¼  14.41, b ¼57.02; R2 ¼ 0.948
Na2SO4: a¼  20.13, b ¼47.35; R2 ¼ 0.887.
181
3.3.2. Effect of cations
The effect of cations on the PIT of o/w emulsions containing
0.4 M concentration of NaCl, KCl, CaCl2 and AlCl3, was also studied
by observing the change in conductivity of the emulsion with
temperature. The purpose was to observe the effect of different
cations on the PIT of o/w emulsion, while having the same
concentration of a specified anion. Fig. 6 shows the effect of
different cations i.e. Na+, K+, Ca2+, and Al3+ on the PIT of o/w
emulsion. It is observed that the PIT of o/w emulsion increases
with an increase in the charge of cations. For the monovalent
cations, i.e. Na+, K+ ions, the salting-out from oil–surfactant–water
interface by breaking of hydrogen bond leads to the destablization
of o/w emulsion. Ca2+ and Al3+ ions form ionic complexes with
both anionic surfactant (SDBS) and salts in the anionic surfactants.
It is observed that o/w emulsion with trivalent cations (Al3+) has
higher PIT than that with bivalent cations (Ca2+). As the charge of
the cations increases, an increase in temperature is needed to
achieve the conversion from the positive spontaneous curvatures
of the surfactant layers to negative curvatures, thereby resulting in
an increase in the PIT of the system (Schott and Royce, 1984). The
PIT of the oil–anionic surfactant–water macro-emulsion system
increases in the following order of cations: Al3+ 4Ca2+ 4 K+ 4 Na+.
3.4. Effect of various inorganic salts on the electrophoretic properties
of the oil–anionic surfactant–water macro-emulsions system
Zeta potential of o/w emulsions using anionic surfactant at
varying concentrations of different salts is shown in Fig. 7. Zeta
potential of o/w emulsion is negatively charged. An increase in the
negative value of zeta potential indicates the stability of o/w
emulsion. This means that the stabilization arises from the mutual
repulsion between the electrical double layer of particles and from
the adsorption of macromolecules at the oil droplets. The negative
surface charge of emulsion droplets resulted from the specific
adsorption of the DBS ion, forming hydrogen bond between the
sulphonate anion and the water molecules in the boundary layer
of o/w emulsion. From Fig. 7, it is observed that the zeta potential
(absolute value) of o/w emulsion decreases with an increase in salt
concentration, which leads to the destabilization of the emulsion.
This is because of the compression of the electrical double layer
around the emulsion droplets which enhances with increasing
ionic strength, and the counter-ion binding between the cations
and the negatively charged emulsion droplets (Ríos et al., 1998).
For mono-valent counter-ions, zeta potential of o/w emulsion
droplets is relatively high as compared to those of multivalent
ð1Þ
Fig. 6. Effect of different cations on the PIT of oil–anionic surfactant–water
emulsion. Different electrolyte concentrations: 0.4 (M) NaCl (―
―); 0.4 (M) KCl
(―○―); 0.4 (M) CaCl2 (―▼―); and 0.4 (M) AlCl3 (―Δ―).
182 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185
Fig. 7. Zeta potential of anionic surfactant–oil–water emulsion system as a function
of salt concentration. Different salts: NaCl (―
―); KCl (―○―); Na2SO4 (―▼―); CaCl2
(―Δ―); and AlCl3 (―■―).
counter-ions. Emulsions with NaCl and KCl have high zeta poten-
tial, leading to formation of stable emulsions. For multivalent
counter-ions, as ionic charge increases, the zeta potential of
emulsion droplets decreases, thereby destabilizing the emulsion.
It is observed that at the same salt concentration, the droplets
containing higher counter-ion charges exhibit lower zeta poten-
tials (Fig. 7). It is evident that as the concentration of AlCl3
increases, the zeta potential of the emulsion, which was very
low, becomes positive and remains close to zero. Thus the
experimental results indicate that the multivalent cationic salts
have greater capability of counter-ion binding than those with
mono-valent cations, following the Schulze–Hardy rule (Ríos et al.,
1998). As shown in Fig. 7, the addition of salts leads to a reduction
in the zeta potential. The decrease in the absolute value of the zeta
potential is usually accompanied by a growth in the effective
diameter of the emulsion droplets. The reduction of the surface
charge of the droplets lowers the electrostatic repulsion between
the droplets, and thus induces coalescence of the droplets.
3.5. Long term stability of emulsion
The stability of the o/w emulsions produced was assessed by
monitoring the change in the droplet size distribution and the
mean droplet size with time of storage at room temperature
(  25 1C). For non-equilibrium systems, the o/w macro-emulsion
has a tendency to reduce its interfacial area and free energy
through several breakdown processes, such as coalescence, cream-
ing or sedimentation and flocculation (Schott, 1973; Solans et al.,
2005). Droplet coalescence is found to be the main mechanism
producing instability of o/w macro-emulsion. Sometimes, Ostwald
ripening may be responsible for droplet growth and possible
instability mechanism of o/w emulsion when kept for a long time.
In coalescence, the interfacial film rupture takes place between
two emulsion droplets when the two droplets collide with each
other forming a new droplet. The inter-droplet forces are mainly
responsible for the rupture of the interfacial film (Egger and
McGrath, 2006). Fig. 8 represents the time-course of growth of
emulsion droplets at a temperature of  25 1C. Droplet growth
curve has two distinct phases. At the beginning of the growth, the
mean size of the droplets increases steadily and rapidly. There-
after, the growth is stifled and the mean size of the emulsion
droplets becomes stable throughout the storage period. The mean
size may be termed as the equilibrium size. For mono-valent ions,
equilibrium droplet size is attained at 45 min. As the charge of
the ions increases, slope of the initial growth phase curve becomes
Fig. 8. Mean droplet size as a function of time for oil–water–anionic surfactant
emulsion system with 0.1 M concentration of various salts at 30 1C: NaCl (―
―); KCl
(―○―); Na2SO4 (―▼―); CaCl2 (―Δ―); and AlCl3 (―■―).
steeper and the equilibrium period for attaining equilibrium
droplet size becomes smaller to 25–30 min. The growth of the
o/w emulsion droplet size with an increase in time may be
attributed to a combination of salting-out and the counter-ion
binding effects of the inorganic salts. Flocculation may also
contribute to the destabilization of the o/w emulsion during the
long-term storage process. The effect of flocculation can be
reduced or eliminated by improving the negative surface charge
on the droplets through tuning of the pH of the system.
O/W emulsion is broken mainly by two mechanisms: coales-
cence and Oswald ripening. For coalescence, the following equa-
tion holds true (Deminiere et al., 1998).
 
1 1 8π
2
¼ 2 ωt ð2Þ
r r0 3
If the experimental data are represented by a linear plot of 1=r 2
versus t, the frequency of rupture per unit of surface of the
emulsion droplet ω can be found straightway. Here r is the average
droplet radius after time t and r0 is the initial droplet radius at
t¼0.
For Oswald ripening, the Lifsitz–Slezov and Wagner (LSW)
theory (Kabalnov and Shchuckin, 1992) provides the following
equation:
 
dr 3 8 C 1 γ V m D
ω¼ ¼ ð3Þ
dt 9 ρRT
If the experimental data fit a linear plot of r 3 versus holding
time during the process of rupture, the ripening rate can be
determined. Here, ρ is the density of the oil phase, γ is the
interfacial tension, D is the diffusion of the dispersed phase in
the continuous phase, C 1 is the bulk phase solubility of an
infinitely large droplet, Vm is the molar volume of the oil phase
and R is the universal gas constant.
In order to test the application of the above theories to the
breakdown of an emulsion, Figs. 9 and 10 were drawn. Both the
aforementioned equations (Eqs. (2) and (3)) predict a linear
variation of rn with time (t). Similar trends were observed by
Uson et al. (2004). The value of n depends on the destabilization
mechanism, i.e., n ¼3 for Oswald ripening and n¼  2 for coales-
cence mechanism. Fig. 9 shows that the curve has two distinct
linear portions. In between these two linear portions, aggregation
or flocculation of droplets may occur. Coalescence may ultimately
lead to flocculation of the droplets following the weakening of the
interfacial film. The rate of coalescence, ω as calculated from the
slope of straight line for the demulsification period, shows an
 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185 183

coalescence and the rate of Ostwald ripening increase with an

increase in the charge of the electrolytes. It is also found that the
initial droplet radius increases with an increase in the valence of
cations of the electrolyte. This confirms the earlier result that the
emulsion with mono-valent cations is more stable and that the
stability decreases with di- and tri-valent cationic electrolytes.
Therefore, it may be surmised that both the coalescence and
Ostwald ripening might have occurred simultaneously.

3.6. Turbidity

The turbidity of an emulsion is a function of the size distribu-

tion of the oil droplets and the droplet concentration. Turbidity of
o/w emulsion decreases due to a lower number of droplets and an
increase in their size because of the coalescence of the droplets.
Fig. 9. Variation of 1/r2 as a function of time for anionic surfactant–oil–water The turbidity can be used to understand the phenomena of
emulsion containing different salts at 0.1 M concentration. NaCl (―
―); KCl (―○―); destabilization of emulsions in the absence of external fields. The
Na2SO4 (―▼―); CaCl2 (―Δ―); and AlCl3 (―■―). turbidity of an emulsion actually signifies the concentration of
droplets present in the emulsion, and it can be used to determine
the oil concentration in the emulsion (Pal, 1994). Fig. 11 shows that
the turbidity of an o/w emulsion decreases with an increase in the
concentration of the electrolyte. This phenomenon can be
explained through the zeta potential of the emulsion.The addition
of an electrolyte lowers the zeta potential of the droplets, and the
emulsions get destabilized. An increase in electrolyte concentra-
tion enhances the destabilization of the emulsion. As a conse-
quence, a creamy layer appears at the top of the turbidity
measurement cell with further coalescence, the demulsification
and the separation of oil and water phases occur (Rios et al., 1998).
For an o/w emulsion with a mono-valent electrolyte (NaCl, KCl),
the destablization effect is lower than that for multivalent
electrolytes.
Fig. 11 shows the variation of turbidity of emulsion as a
function of molar concentration of different mono- and multi-
valent electrolytes. The time-course of turbidity for 0.1 M concen-
Fig. 10. Variation of r3 as a function of time for anionic surfactant–oil–water tration of various electrolytes is shown in Fig. 12. A decrease in
emulsion containing different salts at 0.1 M concentration. NaCl (―
―); KCl (―○―);
turbidity was observed during the beginning of the demulsifica-
Na2SO4 (―▼―); CaCl2 (―Δ―); and AlCl3 (―■―).
tion process, due to a higher number of collisions among oil
droplets. This decrease becomes steeper for multivalent electro-
Table 3 lytes when compared with those of mono-valent electrolytes. The
Coalescence rates and Ostwald ripening rate of oil droplets in o/w emulsion for slope of the turbidity curves (Fig. 11) decreases with time,
different electrolytes. primarily because of a decrease in the number of droplets result-
ing in the lower possibility of coalescence of the droplets. Hence,
Electrolyte Initial droplet Rate of coalescence, Rate of Ostwald
radius, r (μm) ω (μm2/s) ripening, ω (μm3/s) the rate of de-emulsification decreases with an increase in time.
This fact shows that the process is mainly controlled by the
0.1 M NaCl 0.9 0.08 1.077
0.1 M KCl 0.9 0.61 2.489
0.1 M Na2SO4 1.2 1.59 2.712
0.1 M CaCl2 1.8 1.8 123
0.1 M AlCl3 2.4 4.41 308

increase with an increase in the valence of the electrolyte, as can

be seen from Table 3. Therefore, in the beginning, coalescence and
flocculation may be the main instability mechanisms.
Fig. 10 shows a linear dependency of r3 with time. Emulsions
with NaCl, KCl and Na2SO4 show good linearity as predicted by
Eq. (3). But in case of CaCl2 and AlCl3, linear dependency was
poorly exhibited. This indicated that the destablization of emul-
sion occurred by Ostwald ripening. Ostwald ripening arises due to
solubility difference of droplets of different sizes. In Ostwald
ripening, the destabilization causes the larger droplets to grow
at the expense of the smaller ones, probably by molecular diffu-
sion through the continuous phase (Liu et al., 2006). From the Fig. 11. Turbidity of o/w emulsion as a function of electrolyte concentration for
slope of each straight line, Ostwald ripening rate was calculated various electrolytes. Various electrolytes: NaCl (―
―); KCl (―○―); Na2SO4 (―▼―);
(Table 2). From Table 2, it was observed that both the rate of CaCl2 (―Δ―); AlCl3 (―■―).
184 P. Kundu et al. / Chemical Engineering Science 102 (2013) 176–185
Fig. 12. Time course of turbidity for o/w emulsions containing 0.1 M concentration
of various electrolytes. Various electrolytes: NaCl (―
―); KCl (―○―); Na2SO4 (―▼―);
CaCl2 (―Δ―); AlCl3 (―■―).
number of droplet–droplet collisions and can be explained by
Smoluchosky's classical model of rapid flocculation (Tadros and
Vincent, 1985).
4. Conclusions
Oil-in-water (o/w) macro-emulsion was formed by mixing
commercial diesel oil with water in the presence of certain
chemicals and an anionic surfactant, namely sodium dodecyl
benzene sulphonate (SDBS).
From the results of the experimental investigation on the
formation and stability of o/w emulsions, the following conclu-
sions are drawn:

The phase inversion temperature (PIT) of anionic surfactant-o/
w emulsion is found to increase with an increase in surfactant
to oil (s/o) ratio (w/w) for all the electrolytes, namely, NaCl,
Na2SO4, KCl, CaCl2 and AlCl3.

The PIT of o/w emulsion is affected by the type, concentration
and valence of cations of the electrolytes. For the emulsions
having different electrolytes (NaCl and Na2SO4) containing the
same cations (Na+) but different anions (Cl  , SO24  ), the low-
ering of PIT is sharper for the electrolyte with higher ionic
strength than that for the electrolyte with weaker ionic
strength. Bivalent anion, SO24  has more pronounced effect on
the lowering of the PIT than the mono-valent anion, Cl  . The
lowering of PIT occurs because of composite salting-out effect
of the anions and the mono-valent cations.

Multi-valent cations have more pronounced effect than the
mono-valent cations when the anions are the same. The effects
of various electrolytes at a constant concentration of 0.4 M on
the PIT of the o/w emulsion are found in the following order:
AlCl3 4CaCl2 4KCl 4NaCl. This effect is caused by the salting-
in effect of the di- and trivalent cations.

Electrophoretic analysis of o/w emulsion shows that a decrease
in the absolute value of the zeta potential was usually accom-
panied by a growth of the effective diameter of the oil droplets.
The reduction of the surface charge of the oil droplets lowers
the electrostatic repulsion between the droplets, thereby pro-
moting the coalescence of the droplets.

The variations in the droplet size with time indicated that the
droplet coalescence and flocculation are the main mechanisms
of producing instability in o/w macro-emulsion. The coales-
cence theory shows that the holding time needed to break the
drop increases with a decrease in the valence of the cations of
the electrolytes. The rate of coalescence is also larger for higher
valence cations of the electrolytes.

The growth of the oil droplets size in the o/w emulsion with
time may be due to the combination of salting-out effect and
the counter-ion binding effect of the inorganic salts.

The plot of turbidity of the emulsion as a function of time
shows the sequential processes of flocculation, coalescence and
flotation of the oil droplets, once the emulsion has been
broken. Turbidity analysis shows a decrease in the slope of
the turbidity curves (Fig. 8) with time. Hence, the rate of de-
emulsification decreases with time. This fact shows that the
process of de-emulsification is mainly controlled by the num-
ber of droplet–droplet collisions and can be explained by
Smoluchosky's classical model of rapid flocculation.
Acknowledgements
We thankfully acknowledge the financial support provided by
the Ministry of Human Resources Development (MHRD), Govern-
ment of India for carrying out this study. We also wish to
acknowledge the assistance provided by the Centre of Excellence
in Nanotechnology, IIT Roorkee in the measurement of zeta
potential. Sincere thanks are also due to the Reviewers for their
insightful comments.
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