5808 Ind. Eng. Chem. Res.

2010, 49, 5808–5815

Stability and Performance Study of Water-in-Oil-in-Water Emulsion: Extraction

of Aromatic Amines
Jaydeep M. Barad
Department of Chemical Engineering, S. V. National Institute of Technology, Surat-395 007, Gujarat, India

Mousumi Chakraborty and Hans-Jörg Bart*

Department of Mechanical and Process Engineering, UniVersity of Kaiserslautern, 67663 Kaiserslautern, Germany

One of the major obstacles to the application of emulsion liquid membranes to industrial separations is the
stability of emulsion globules. Stability of emulsion is affected by two phenomenasglobule rupture and osmotic
swell. Interfacial shear between the continuous and membrane phase causes the liquid membrane to thin and,
in some cases, rupture, thereby affecting separation. Destabilization phenomena affecting the homogeneity of
dispersions are emulsion globule migration (creaming, sedimentation) and size variation or aggregation
(coalescence, flocculation). In the present study, the stability of an emulsion liquid membrane is studied by
varying different parameters, for example, internal acid phase and surfactant concentration and stirrer speed
for emulsification. Dispersion destabilization of the emulsion is detected by Turbiscan. Properties such as
interfacial tension, drop size distribution, photomicrographs, and zeta potential are also analyzed to evaluate
emulsion stability. A stable emulsion is used for the removal of aromatic amines from aqueous solutions. An
advancing reaction front model considering competitive transport of aromatic amines has been proposed to
simulate data. The simulated curves are found to be in good agreement with the experimental data.

Introduction mechanisms8 which include (i) coalescence of the internal

Aromatic amines such as aniline and its derivatives are an
important class of environmental water pollutants.1 They are
widely used in the manufacture of azo dyes, rubbers, plastics
cosmetics, pharmaceuticals, and pesticides. Hence, aromatic
amines constitute a group of priority water pollutants which
are present at high concentrations in groundwater, and soils
nearby many industrial contaminated zones have to be ef-
fectively removed.2,3Several attempts have been made either
to treat such types of effluents for facilitating easy disposal or
to recover the chemicals and recycle the process water.
Traditional method of purification such as, distillation, liquid
extraction, and absorption are still in use; however, industries
are looking for competing alternative technologies which may
overcome some of the inherent disadvantages of the traditional
processes.
The liquid membrane (LM) separation technique provides a
potentially powerful technique for affecting a diverse number
of separation operations. Aromatic amines had been successfully
removed from wastewater by a number of researchers using
emulsion liquid membranes (ELMs).4,5 Devulapalli and Jones6
separated 99.5% of the aniline within 4 min in a standard
Rushton stirred tank using kerosene and sorbitan monooleate
(span 80) as the membrane phase and hydrochloric acid as the
internal phase. Datta et al.7 also studied the removal of aniline
from an aqueous solution in a mixed flow reactor. The maximum
removal of aniline obtained in this study was 98.53%.
Although all of them achieved 98-99% separation efficiency,
the problem that inhibits the application of this technology in
industrial equipment is the loss of extraction efficiencies that
often occur in these systems due to lack of stability of the
emulsion globules. The breakdown of water-in-oil-in-water (w/
o/w) type dispersions is described through several possible
* To whom correspondence should be addressed. Tel.: +49
6312052414. E-mail: bart@mv.uni-kl.de.
10.1021/ie901698u  2010 American Chemical Society
Published on Web 05/11/2010
aqueous droplets into larger internal droplets, (ii) coalescence
of the emulsion globules suspended in the external continuous
phase, (iii) expulsion of the internal droplets following rupture
of the thin membrane film during interaction of the internal and
external continuous phases, and (iv) swelling or contraction due
to water permeation through the oil membrane by diffusion in
the case of w/o/w emulsions.
The first study on stability was performed experimentally by
Hochhauser and Cussler.9 They used 0.l M sodium dichromate
solution as the internal phase and water as the external bulk
phase with span 80 as the surfactant dissolved in an organic
membrane phase. The solubility of dichromate found in the
external water phase was due to the rupture of the membranes.
They observed a rapid breakage during an initial period with
no further breakage at longer times. Martin and Davies10 along
with their mass transfer studies on the extraction of copper from
an aqueous solution also performed a stability study using
sulfuric acid as the encapsulated phase. Their study revealed
that the emulsion breakup was dependent on factors like the
operation conditions in the mixing device, size of the subdrops,
type of surfactant used, and impeller speed. Breakage was also
found to increase linearly with time. This was however in
contrast to the findings of Kondo et al.11 and Takahasi et al.;12
all measured the stability of double emulsions using a tracer
technique. The effects of variables like tracer or salt concentra-
tion, agitation time, size of the emulsion drops, concentration
of the emulsifying agent, and pH of the internal droplets on
breakage were studied in the above investigations. Shere and
Cheung13 measured the stability of ELMs as a function of time
using NaOH as a tracer and span 80 as the surfactant. Stroeve
et al.14 used this approach on the study of Taylor15 who was
the first to study both experimentally and theoretically the
deformation and breakup of a drop of a Newtonian liquid
suspended in another immiscible Newtonian liquid undergoing
simple shear and plane hyperbolic flows. Similar studies had
 Ind. Eng. Chem. Res., Vol. 49, No. 12, 2010 5809

Figure 1. BS profile at different internal phase acid concentrations.

been conducted experimentally by Grace et al.16 Bart et al.17 et al.20 and Kasaini et al.21 also used the tracer technique to
found that osmotic swelling can create a breakdown of study emulsion stability. Mengual et al.22 proposed physical
membrane stability and revealed the water transport mechanism models for the surface flux in the backscattered spot light and
has its origin in reversed micelles dissolved in the LM.18,19 Goto the diffuse reflectance measurement performed with the Tur-
5810 Ind. Eng. Chem. Res., Vol. 49, No. 12, 2010
Figure 2. Effect of surfactant concentration on interfacial tension and the
mean diameter of the internal droplets.
Figure 3. Effect of surfactant concentration on internal droplet size
distribution (log-normal).
biscan MA 1000 optical analyzer. Yan et al.23 monitored osmotic
swelling behavior over a long period of time (up to about 4 h)
for a w/o/w system. The osmotic pressure difference between
the internal and external aqueous phases was induced by creating
a concentration difference of D-glucose between the two aqueous
phases. Chakraborty et al.24 found that the leakage phenomena,
which reflect the stability, are influenced by pH of the feed
phase, speed of agitation, emulsion drops size per unit specific
interfacial area, surfactant concentration, pH in inner aqueous
phase, and the presence of different tracers. Chakraborty and
Bart25 also found that the dispersed drop sizes as well as internal
droplets sizes define the interfacial contact area and are
important in determining efficiency of extraction and stability
of the liquid membrane. Liu et al.26 found that the main
destabilization mechanism of the nanoemulsion systems was
Ostwald ripening. They also observed that the effect of
flocculation can be reduced or eliminated by improving the
negative surface charges on the droplets through tuning the pH
of the systems.
There still exists some scope for better insight to study,
monitor, and predict the emulsion stability. In the present study,
Turbiscan has been used to monitor emulsions and dispersions
in the kinetic studies of emulsion stability. Properties such as
interfacial tension, drop size distribution, photomicrographs and
zeta potential are also analyzed to evaluate emulsion stability.
A stable emulsion comprising n-heptane as the membrane phase
with span 80 as the surfactant and dilute hydrochloric acid as
the internal phase is used for the removal of aromatic amines
from a synthetic binary feed mixture as well as from industrial
wastewater. An advancing reaction front model considering
competitive transport of aromatic amines has been proposed to
simulate solute transport data.
Experimental Procedure
Chemicals. Span 80 (sorbitan monooleate) as surfactant,
n-heptane as membrane phase, and hydrochloric acid (all purity
greater than 0.99 mass fractions) as internal phase are used for
ELMs preparation. Aniline and 4-chloro aniline (supplied by
Glaxo India, Ltd.) are used to prepare a synthetic feed mixture.
Common effluent treatment plant (Palsana, India) wastewater
(more than 200 numbers of dying houses) is used as industrial
wastewater. Nessler reagent (supplied by Finar chemicals) is
used to detect ammonical nitrogen in industrial wastewater.
Apparatus and Procedure. The internal phase (1 N HCl)
and membrane phase (n-heptane and span 80) are emulsified
using an ultraturax T25 homogenizer (IKA, Germany), a high
speed mechanical stirrer, with speed variation from 6500 to
24000 rpm. Emulsion stability is checked varying different
parameters, and the stable emulsion is then dispersed in the feed
phase. The agitation speed of the mixer is controlled by a speed
controller and monitored by a tachometer. Samples of about 2
mL are withdrawn from the extractor at different intervals of
time and are filtered through a sintered glass plug to separate
emulsion and feed phase and then analyzed.
The concentrations of aromatic amines in feed phase are
measured at characteristic wavelengths using a Hach (Germany)
make UV-vis spectrophotometer.
Measurement of Physical Properties of the Emulsion.
Interfacial tensions are measured by the Du Noüy ring method
with a tensiometer. The lower phases are hydrochloric acid
solutions (inner phase) in all cases at different concentrations.
The concentration of surfactant (span 80) in n-heptane (mem-
brane phase) is varied in the upper phase. Oil and water phases
are equilibrated before the interfacial tension measurements.
Emulsion stability is analyzed using transmission and back-
scattering (BS) profiles, scanning the emulsion sample by light
rays of 880 nm wavelength using Turbiscan classic MA 2000
(Formulaction, France).
Dispersed drop size measurements are carried out within a
few minutes after preparation of the emulsion. Samples (1 mL)
are taken and diluted in an aqueous phase (3 mL). To improve
the optical transparency of the dispersed emulsion, most of the
emulsion drops are adsorbed by contacting the drop with filter
paper, leaving few emulsion drops on the glass slide. The
photomicrographs are taken using Diastar Microscope and
Photostar camera system (Cambridge Instruments, USA).
Internal droplets size and drop size distribution of the (w/o)
emulsion are measured by an acoustic and electroacoustic
spectrometer (model DT1200, Dispersion Technology, Inc.,
USA). Colloidal silica solution (Silica Ludox, wt fraction 10%)
having a mean particle diameter 28 ( 5 nm was used for
calibration.
The zeta-potential measurements were performed using the
electrophoretic light scattering method (ELS-8000, Photal
Otsuka Electronics Co. Ltd., Osaka, Japan).
Mathematical Model. The model has been derived from the
advancing front model of Ho et al.27 and neglects the external-
phase mass-transfer resistance and the effect of membrane
breakage. Following the work of Chakraborty et al.28,29 the
 Ind. Eng. Chem. Res., Vol. 49, No. 12, 2010 5811
advancing front model in dimensionless form can be written
as
∂g 1 ∂ 2 ∂g
∂τ
)
(1 - φ)η 2 ∂η
η
∂η ( ) (1)

∂g' β ∂ 2 ∂g'
∂τ
) η
(1 - φ)η2 ∂η ∂η
( ) at (χ < η < 1, τ > 0) (2)

τ ) 0, g ) 0, g' ) 0 (η e 1) (3)
η ) χ, g ) 0, g' ) 0 (τ g 0) (4)
η ) 1 then g ) CDh, g' ) CD′ h' at (τ g 0) (5)

Here eq 1 gives the solute balance for aniline and eq 2 for

4-chloroaniline, respectively. The material balance equations in
the external phase are then
dh ∂g
) -E η)1 (6)
dτ ∂η

dh' ∂g'
) -Eβ η)1 (7)
dτ ∂η

τ ) 0, h ) 1, h' ) 1 (8)
The material balance equation at the reaction front is as follows:
dχ 1 ∂g β ∂g'
- ) + (9)
dτ φm ∂η η)χ φm' ∂η η)χ

τ ) 0, χ)1 (10)
The coupled eqs 1, 2, 6, 7, and 9 were solved by numerical
computation using an implicit finite difference technique.
Distribution coefficients are calculated by a linear regression
method. A central difference scheme has been used for
integration along the dimensionless radial distance. The grid
sizes in τ and χ directions have been chosen by trial and error
to obtain good convergence.
The diffusivity values of the aniline and 4-chloroaniline in
the membrane phase is determined by the correlation of Wilke
and Chang30 and found to be 5.976 × 10-10 and 5.466 × 10-10
m2/s, respectively. The Sauter mean diameter is found to be
0.1 cm.31

Results and Discussion

It has been found from the literature that more than 90-99%
recovery of aromatic amine is possible within 20 min of
residence time.5-7 The BS profile of any sample scanned from
the bottom (0 mm) to the top of the vial (∼60 mm) during the
period of 20 min shows that the top part of the emulsion sample
has shown some changes probably due to the release of bubbles.
However, the middle and the bottom part of the sample have
not changed noticeable.
Effect of Internal Phase Acid Concentration. At a surfac-
tant concentration at 5.0% w/v, an S value (ratio of the volume
of the surfactant solution to that of the internal phase in
emulsion) at 0.5, and an ultraturax speed at 6500 rpm the internal
phase acid concentration is varied from (0.1-1.0 N). It is found
from Figure 1 that with variation in the concentrations of the
internal phase (0.1-1.0 N) the BS increases. It indicates that Figure 4. BS profile at different surfactant concentration.
the emulsion has become denser with an increase in internal
phase acid concentration. Actually the size of the emulsion Then the migration velocity of emulsions is calculated from
globule increases with an increase in internal phase acid the clarification front obtained from transmission profiles.
concentration due to swelling which decreases emulsion stability. Emulsions with 0.1 and 0.5 N internal phase acid concentration
5812 Ind. Eng. Chem. Res., Vol. 49, No. 12, 2010

Figure 5. BS profile at different stirrer speeds.

 Ind. Eng. Chem. Res., Vol. 49, No. 12, 2010 5813

Figure 6. Photomicrograph of emulsions prepared at (a) 6500, (b) 9500,

and (c) 13500 rpm.

show better stability (migration rates, 0.248 and 0.276 mm/min)

than the emulsion with 1.0 N internal phase acid concentration
(migration rate, 0.321 mm/min). Inspite of the slight instability
problem, internal phase acid concentration is kept at 1.0 N
because a high H+ concentration increases the capacity of the
internal phase as a sink for amine compounds.
Effect of Surfactant Concentration. Figure 2 shows that
interfacial tension decreases with increasing surfactant concen-
tration, and there is no change of interfacial tension when the
surfactant concentration reaches its optimum value; that is, the Figure 7. Effect of stirrer speed on internal droplet size distribution (log-
critical micelle concentration (CMC) of span 80 in n-heptane normal and cumulative).
is 3.16 × 10-4 mol/L (0.135 g/L).32 It is observed that the
surfactant concentration in the membrane phase significantly
affects the emulsion stability. With increasing surfactant con-
centration, interfacial film strength will increase and enhance
resistance to coalescence.
The droplet size distribution and mean droplet diameters of
emulsions with different surfactant concentrations are presented
in Figures 2and 3. Emulsions containing low surfactant con-
centrations (0.5% w/v) are not very stable and result in phase
separation within a short period of time. The droplet size
distribution becomes narrow, and the mean droplets diameter
declines from about 3.13 to 1.96 µm as the surfactant concentra-
tion increases from 1.0 to 4.0% w/v and then again increases
slightly with surfactant concentration due to the creaming effect.
Therefore, in the remainder of the experiments the surfactant
volume was kept at 5.0% w/v to provide a stable emulsion with
a narrow drop size distribution (Figure 3).
The BS profile (Figure 4) indicates that the sizes of the
emulsion globules have been increased with an increase in
surfactant concentration. When the surfactant concentration is
5.0% w/v and higher than what is due to the creaming effect
and high viscosity of the emulsion, a rapid swelling of internal Figure 8. Zeta potential as a function of pH with 5.0% (w/v) surfactants
droplets occurs which results in an increase in globule sizes. concentration.
Effect of Stirrer Speed. Keeping other parameters constant,
emulsions are prepared at 6500, 9500, and 13500 rpm of agitation rate used to prepare the emulsion. From Figure 7,
ultraturax. The percent BS at 6500 rpm is higher than that at which shows log-normal as well as cumulative internal droplet
9500 rpm, but both emulsions are found stable (Figure 5). The size distribution, it has been observed that emulsions prepared
emulsion prepared at 13 500 rpm stirrer speed is found unstable using 6500 and 9500 rpm result in a narrow size distribution
as the BS profile is moving upward with time. The migration having internal droplets mean diameters of 2.08 and 1.17 µm.
velocity of the clarification front of the 13 500 rpm emulsion is In contrast, the emulsion prepared at 13 500 rpm yields broader
also very high (1.24 mm/min). Actually with increasing stirrer droplet size distribution with a lower mean diameter of 0.042
speed, the diameter of the internal droplets will decrease and µm.
population density will increase which leads to flocculation and Long-Term Stability. For molecules and particles that are
coalescences of an emulsion. From the microphotograph (Figure small enough, a high zeta potential will confer stability, that is,
6) and internal droplet size distribution (Figure 7), it is found the solution or dispersion will resist aggregation. When the
that diameters of the droplets in dispersed emulsions are in the potential is low, attraction exceeds repulsion and the dispersion
range of 10-110 µm and those of the internal droplets are in will break and flocculate. So, colloids with high zeta potential
the range of 0.001-10 µm. However, the dispersed emulsion (negative or positive) are electrically stabilized, while colloids
drops prepared at 6500 rpm contain a relatively less number of with low zeta potentials tend to coagulate or flocculate.
internal droplets (Figure 6a) than those prepared at 9500 rpm Here droplets of the emulsions are found to be negatively
(Figure 6b). Distefano et al.33 found that the number and size charged, as shown in Figure 8. The zeta potential of the emulsion
of internal droplets in multiple emulsions are a function of the is approximately -8.8 mv at pH 6.8 (water as internal phase).
5814 Ind. Eng. Chem. Res., Vol. 49, No. 12, 2010

the residence time, the better is the solute recovery. But longer
residence time increases water transport, which ultimately
diminishes the solute enrichment in the internal phase. Swelling
and globule rupture can be controlled by proper selection of
emulsion composition and parameters during the emulsification
process. This paper describes the stability behavior of emulsions
under a wide variety of operating conditions such as internal
acid phase and surfactant concentration and stirrer speed for
emulsification. From this study it has been found that a
uniformly distributed stable emulsion can be obtained by
selecting optimum conditions which will provide a higher mass
transfer rate and high extraction efficiency for the removal of
aromatic amines from the binary feed mixture as well as from
industrial wastewater.

Acknowledgment
The authors wish to acknowledge the Alexander von Hum-
boldt-Stiftung Foundation, Germany, for financial support.

Figure 9. Variation of external phase aniline and 4-chloroaniline concentra-

tions with time. Nomenclature
C, C′ ) aromatic amines (aniline and 4-chloroaniline) concentra-
Liu et al.26 suggested that negative charges on the droplets come tions in saturated zone of emulsion globule, mol/L
from the adsorption of hydroxyl ions at the o/w interface, and Cio ) initial internal reagent concentration in internal phase, mol/L
the ethylene oxide (EO) group of span 80 creates hydrogen Ci ) internal reagent concentration in internal phase, mol/L
bonds with the hydroxyl ions to give more negative surface Ce, Ce′ ) aromatic amines concentration in external phase, mol/L
charges. The zeta potential is strongly dependent on the pH of ′ ) initial aromatic amines concentration in external phase,
Ceo, Ceo
the system. The absolute value of the zeta potential is reduced mol/L
with the decrease of pH. At pH 3.8, the zeta potential is close D, D′ ) diffusivity of aromatic amines in saturated zone of emulsion
to zero, after which the droplets become positive charged (+16.8 globules, m2/s
mv at pH 1.0) with 1 N HCl as the internal phase. With 1 N V ) total volume of emulsion phase, L
NaOH as the internal phase, the absolute value of the zeta Ve ) volume of external phase, L
potential increases to -18.2 mv at pH 12. CD, C D′ ) distribution coefficients of the solutes (aniline and
Low zeta potential value,+ 16.8 mv (below +20 mv), indicates 4-chloroaniline) between membrane and external phase
instability of emulsion particularly when we are considering long- r ) radial coordinate in emulsion globules, m.
term stability. Abu-Nemeh and Peteghem34 studied the aging of R ) radius of emulsion globules, m
the membrane phase and found span 80 in the presence of water Rf ) reaction front position, m
and traces of hydroxyl ions or hydrogen ions undergoes hydrolysis t ) time, s.
but up to 20 min of residence time no significant changes of ELM ) emulsion liquid membrane
emulsion properties have been observed. K ) ratio of the volume of the feed phase to that of the emulsion
Extraction of Aromatic Amines. Using optimum conditions PSD ) particle size distribution
(internal acid concentration, 1.0 N; span 80 concentration, 5.0% S ) ratio of the volume of the surfactant solution to that of the
(w/v); and 6500 rpm) a stable emulsion is prepared, which is used internal phase in emulsion
for the removal of aniline and 4-chloroaniline mixtures (100 ppm BS ) back scattering
each) from aqueous solutions. The values of S (ratio of the volume Variables
of the surfactant solution to that of the internal phase in emulsion)
C C'
and K (ratio of the volume of the feed phase to that of the emulsion) g) , g' )
are fixed at 0.5 and 8, respectively. It is found that 94% recovery Ceo ′
Ceo
(maximum) of aniline is possible, along with 89% 4-chloroaniline Ce Ce′
h) , h' )
within 20 min of residence time (Figure 9). Figure 9 shows that Ceo ′
Ceo
initially experimental and simulated data superimpose, but with Ci Ci′
time, a deviation is observed because of a slight membrane m) , m' )
Ceo ′
Ceo
breakage problem only. Membrane breakage starts initially and
continues to progress with time.
Common effluent treatment plant wastewater has been treated Greek Letters
with stable ELMs and significant reduction (98%) of ammonical η ) r/R, χ ) Rf/R,
nitrogen has been observed. E ) 3V/Ve, τ ) D t/R2, β ) D′/D
φ ) volume fraction of internal aqueous phase in the emulsion

Conclusions
Emulsions become unstable due to osmotic swelling and
globule rapture, thereby affecting mass balances and final
concentrations of the solute in the external phases. Residence
time is the key parameter of the ELM process. The longer is
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ReceiVed for reView October 29, 2009
ReVised manuscript receiVed April 20, 2010
Accepted April 27, 2010
IE901698U