Langmuir 2008, 24, 3061-3069 3061

Contribution of Molecular Pathways in the Micellar Solubilization of

Monodisperse Emulsion Droplets
Suwimon Ariyaprakai and Stephanie R. Dungan*
Department of Food Science and Technology, Department of Chemical Engineering and Materials Science,
UniVersity of California, DaVis, One Shields AVenue, DaVis, California 95616

ReceiVed October 15, 2007. In Final Form: December 8, 2007

It is often proposed that oil solubilization in anionic and nonionic micelles proceeds by different mechanisms, with
diffusion of the oil molecule thought to control the former, and the latter interfacially controlled. In order to investigate
this hypothesis, the effect of aqueous phase viscosity, salt, and surfactant concentration during the solubilization
process was studied. The progressive decrease in average droplet size of nearly monodisperse emulsions during
solubilization in SDS or Tween 20 micellar solutions was monitored by light scattering, and the change in turbidity
was measured by UV-vis spectrophotometer. The solubilization rates were analyzed using a population balance
approach to calculate the mass transfer coefficients. Increasing the aqueous viscosity by adding sucrose reduced the
mass transfer coefficients of n-tetradecane and n-dodecane but had a smaller effect on n-hexadecane. The strong
dependence of the solubilization rate for the shorter chain length alkanes on aqueous viscosity supported a mechanism
in which the oil undergoes molecular diffusion before being taken up by micelles. The dependence of the solubilization
kinetics on surfactant concentration appeared consistent with this mechanism but yielded a slower micellar uptake
rate than previously predicted theoretically. As the solute chain length increased in nonionic surfactant solutions, an
interfacial mechanism mediated by micelles appeared to contribute substantially to the overall rate. Addition of salt
only slightly increased the solubilization rate of n-hexadecane in SDS solutions and, thus, indicated a weak role of
electrostatic interactions for ionic surfactants on the overall mechanism.

Introduction
Oils such as long-chain alkanes are normally insoluble or only
slightly soluble in water. In the presence of surfactant micelles,
oil transfers into these micelles in a solubilization process, and
therefore, the aqueous oil solubility is increased significantly.
This process is important in many areas such as detergency, drug
and flavor delivery, emulsion stability, and biological absorption
of hydrophobic compounds.1-5 As shown in Figure 1, two
alternative pathways for oil to be solubilized into micelles,
molecular (pathway I) and micelle-mediated (pathway II), have
been proposed and debated. In the first, oil molecules must diffuse
individually away from the oil/water interface before being taken
up by surfactant micelles; while in the latter, there must be a
direct detachment of surfactant micelles at the oil/water interface
for micelles to take up the oil molecules.
In one of the first studies of these mechanisms, Chan et al.6
investigated the effect of convection on the rate of fatty acid
dissolution from a solid disc into ionic surfactant solutions. The
micelle-mediated pathway was assumed to be controlling, and
it was theoretically analyzed by considering five mechanistic
steps in series: micelle diffusion to the fatty acid/water interface,
micelle adsorption at the interface, filled micelle formation as
the fatty acid is incorporated into micelles, filled micelle
desorption from the interface, and filled micelle diffusion into
the water continuum. The solubilization rate measured from
experiments was most consistent with their theoretical predictions
for control by the rate at which the filled micelle desorbs/diffuses.
* To whom correspondence should be addressed. Tel.: 1-530-752-5447.
Fax: 1-530-752-4759. E-mail: srdungan@ucdavis.edu.
(1) Borel, P. Clin. Chem. Labor. Med. 2003, 41, 979.
(2) Crisp, M. T.; Tucker, C. J.; Rogers, T. L.; Williams, R. O.; Johnston, K.
P. J. Controlled Release 2007, 117, 351.
(3) Kabalnov, A. S. Langmuir 1994, 10, 680.
(4) Patist, A.; Kanicky, J. R.; Shukla, P. K.; Shah, D. O. J. Colloid Interface
Sci. 2002, 245, 1.
(5) Torchilin, V. P. Pharm. Res. 2007, 24, 1.
(6) Chan, A. F.; Evans, D. F.; Cussler, E. L. AIChE J. 1976, 22, 1006.
Figure 1. Two proposed pathways for oil molecules to transfer
from an emulsion droplet into an aqueous micellar solution.
Carroll7 measured the solubilization rate of a single oil drop,
attached to a fiber in aqueous nonionic surfactant solutions. He
also supported a micelle-mediated pathway as the primary
mechanism. Carroll7 further proposed that the time required for
demicellization determines the rate at which surfactant is supplied
to the oil drop interface and that this surfactant adsorption process
controls the overall solubilization kinetics. Using the same drop-
on-fiber technique, Ward8 obtained experimental results that
agreed with the mechanism proposed by Carroll, for the case of
oils with low water solubility (<10-6 wt %), such as alkanes
with 12 or more carbons. For oils with higher aqueous solubility,
however, the molecular diffusion pathway was suggested to be
increasingly important.
Prak et al.9 also proposed that an interfacial, pathway II
mechanism controlled the solubilization of n-octane, n-decane,
and n-dodecane in micelle solutions. They found that the measured
mass transfer coefficient increased with decreased oil solute size,
increased surfactant chain length, and decreased micelle capacity.
They found these results to be consistent with a mechanism in
(7) Carroll, B. J. J. Colloid Interface Sci. 1981, 79, 126.
(8) Ward, A. J. I. Proc. R. Ir. Acad. 1989, 89B, 375.
(9) Prak, D. J. L.; Abriola, L. M.; Weber, W. J.; Bocskay, K. A.; Pennell, K.
D. EnViron. Sci. Technol. 2000, 34, 476.

10.1021/la703204c CCC: $40.75 © 2008 American Chemical Society

Published on Web 03/07/2008
3062 Langmuir, Vol. 24, No. 7, 2008
which micelles collide with and dock at the interface, with the
subsequent uptake of solute from the drop controlling the overall
rate. This mechanism is similar to one proposed for water-in-oil
microemulsions incorporating proteins10 or amino acids.11 Chen
et al.12 and Kralchevsky and co-workers13,14 also explained their
experimental observations with this mechanism for n-hexadecane
and triglyceride oils. These works9,12,13 were mainly focused on
nonionic surfactants.
By contrast, Kabalnov3 strongly supported the dominant role
of the molecular diffusion pathway (I) for solubilization in ionic
surfactant solutions. He based his conclusions on an observed
independence of Ostwald ripening rate on micelle concentration.
He suggested that the electrostatic repulsion between surfactants
adsorbed on the oil/water interface and the micelle headgroups
eliminated the possibility of a micelle-mediated interfacial
pathway (II). Later, Kabalnov and Weers,15 Dungan et al.,16
Todorov et al.,17 and Sailaja et al.18 examined theoretical
approaches to describe quantitatively this reaction-enhanced
(pathway I) mechanism.
The objective in this work is to gain more information about
the importance of the molecular diffusion pathway during the
solubilization process into either ionic or nonionic micelles by
studying the effect of the viscosity and surfactant concentration
on solubilization kinetics. Previously, Chen et al.12 and Dungan
et al.16 increased viscosity by adding a water-soluble polymer
and found that the enhanced viscosity did not reduce the
solubilization rate in nonionic surfactant solutions. However,
although the presence of dissolved polymer would strongly hinder
the diffusion of colloidal bodies such as micelles, it would have
only a small influence on the diffusion of low-molecular-weight
compounds such as the solute.19 Thus, in the present research,
the effect of viscosity was investigated using sucrose in
monodisperse alkane-in-water emulsions that were gradually
solubilized in an aqueous micellar solution. As a low-molecular-
weight compound, sucrose has the ability to retard the movement
in water of the transferring solute in its molecular form.20 By
using a nearly monodisperse emulsion, the rate at which the size
of the oil droplet diminishes could be monitored,21 and combined
with turbidity measurements to provide two approaches to
measure the solubilization rate. These experiments were con-
ducted in both anionic and nonionic micellar solutions.
This study also examines the relationship between solubili-
zation flux and surfactant concentration, which plays a predicted
role in the molecular pathway mechanism. In pathway I, increased
surfactant concentration is expected to enhance the flux of solute
into the micellar solution as φmic1/2, where φmic is the volume
fraction of micelles in solution. We examine this prediction in
the present work, and compare our findings to models given in
Kabalnov and Weers.15
(10) Dungan, S. R.; Bausch, T.; Hatton, T. A.; Plucinski, P.; Nitsch, W. J.
Colloid Interface Sci. 1991, 145, 33.
(11) Plucinski, P.; Nitsch, W. J. Phys. Chem. 1993, 97, 8983.
(12) Chen, B. H.; Miller, C. A.; Garrett, P. R. Colloids Surf. A: Physicochem.
Eng. Aspects 1997, 128, 129.
(13) Christov, N. C.; Denkov, N. D.; Kralchevsky, P. A.; Broze, G.; Mehreteab,
A. Langmuir 2002, 18, 7880.
(14) Kralchevsky, P. A.; Denkov, N. D.; Todorov, P. D.; Marinov, G. S.;
Broze, G.; Mehreteab, A. Langmuir 2002, 18, 7887.
(15) Kabalnov, A.; Weers, J. Langmuir 1996, 12, 3442.
(16) Dungan, S. R.; Tai, B. H.; Gerhardt, N. I. Colloids Surf. A: Physicochem.
Eng. Aspects 2003, 216, 149.
(17) Todorov, P. D.; Kralchevsky, P. A.; Denkov, N. D.; Broze, G.; Mehreteab,
A. J. Colloid Interface Sci. 2002, 245, 371.
(18) Sailaja, D.; Suhasini, K. L.; Kumar, S.; Gandhi, K. S. Langmuir 2003,
19, 4014.
(19) Contreras-Lopez, E.; Champion, D.; Hervet, H.; Blond, G.; Le Meste, M.
J. Agric. Food Chem. 2000, 48, 1009.
(20) Covarrubias-Cervantes, M.; Champion, D.; Debeaufort, F.; Voilley, A.
J. Agric. Food Chem. 2005, 53, 6771.
Ariyaprakai and Dungan
For cases where pathway II contributes to the solubilization
mechanism, certain elements of the mechanism could be strongly
affected by electrostatic repulsion, such as surfactant adsorption
to the emulsion interface. To assess the role of these interactions
during solubilization in ionic surfactants, the effect of addition
of salt on the solubilization rate of n-hexadecane into SDS aqueous
solutions was also investigated. Addition of salt should strongly
reduce electrostatic repulsion and, thus, accelerate steps limited
by such repulsion.
Materials and Methods
Materials. n-Hexadecane, n-tetradecane, and n-dodecane with
>99% purity were purchased from Sigma-Aldrich (St. Louis, MO).
Sodium dodecyl sulfate (Ultrapure) was obtained from USB
Corporation (Cleveland, OH). Both Tween 20 and sodium chloride
(certified ACS crystal) were obtained from Fisher Scientific
(Pittsburgh, PA). Sucrose (granulated white pure cane sugar) was
supplied by C&H Sugar Company (Crockett, CA). Deionized water
was passed through an Ultrapure ion exchange filter (Barnstead
Corporation, Dubuque, IA) before use.
Emulsion Preparation. An alkane-in-water stock emulsion,
consisting of 20 wt % alkane and 0.2 wt % SDS or 0.6 wt % Tween
20, was prepared by first mixing these in water with a high-speed
blender (Ultra-turrax T25, IKA Labortechnik, Germany) and then
further homogenizing with a high-pressure laboratory homo-
genizer (Mini-Lab, type 8.30H, Rannie, Denmark) at a pressure of
200-400 bar. The stock emulsion was fractionated22 to be nearly
monodisperse with various mean sizes to yield a span ∼0.5-0.6
or a relative standard deviation ∼19-23%. Surfactant above the
critical micelle concentration (cmc) was added directly to the emulsion
in order to induce depletion forces between larger droplets in the
system. These largest emulsion droplets flocculated and creamed,
while smaller ones were left below. A separatory funnel was used
to separate the two layers. The same procedure was repeated with
both cream and bottom layers until an emulsion with a desirable
narrow size distribution was obtained. The added surfactant con-
centrations, and hence the strength of the depletion force, was
varied and adjusted, to yield the desired result. A more detailed
description of this procedure is described by Ariyaprakai and
Dungan.21
The wt % of oil in the obtained monodisperse emulsion was
determined by measuring the density of emulsion at room temperature
using a 1-mL pycnometer (Thomas Scientific, Swedesboro, NJ).
For solubilization experiments, the obtained concentrated mono-
disperse emulsion was diluted to ∼0.04 wt % oil with an aqueous
surfactant solution without additive, a solution with 30 wt % sucrose,
or one with 100-300 mM sodium chloride. Surfactant concentrations
in the range 1-4 wt % were employed. This diluted emulsion was
kept in a plastic bottle in a water bath at 30 ( 1 °C (n-hexadecane
or n-tetradecane) or at room temperature of 22 ( 1 °C (n-dodecane)
for turbidity and light-scattering measurements. We note that for
n-hexadecane and n-tetradecane the temperature was controlled at
30 °C in order to be consistent with our previous studies.16,21,23
However, for n-dodecane, the experiment was much faster and
occurred within 1 h; thus, the sample cuvette was retained in the
UV-vis spectrophotometer without temperature control for the whole
experimental period.
The control experiment in which emulsion was diluted with water
(no added surfactant) showed that both emulsion droplet size and
turbidity did not change for the entire experimental period. This
confirmed that there were negligible levels of excess micelles in the
emulsion after fractionation and dilution and, thus, no measurable
solubilization occurred without added surfactant. The result also
provided evidence of the stability of our emulsion system, since no
coalescence or Ostwald ripening was detected.
(21) Ariyaprakai, S.; Dungan, S. R. J. Colloid Interface Sci. 2007, 314, 673.
(22) Bibette, J. J. Colloid Interface Sci. 1991, 147, 474.
(23) Tai, B. H. The Kinetics of Solubilization and Transport by Micelles in
Oil-in-Water Emulsions. M.S. Thesis, University of California, Davis, 1999.
Solubilization of Monodisperse Emulsion Droplets Langmuir, Vol. 24, No. 7, 2008 3063

Figure 2. Solubilization kinetics of nearly monodisperse hexadecane-in-water emulsions as a function of time into 3 wt % Tween 20 micellar
solutions with and without sucrose. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial
concentration in emulsion. Initial emulsions contained 0.04 wt % hexadecane. Curves are fits with the population balance model.

Figure 3. Solubilization kinetics of nearly monodisperse tetradecane-in-water emulsions as a function of time into 3 wt % Tween 20 micellar
solutions with and without sucrose. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial
concentration in emulsion. Initial emulsions contained 0.04 wt % tetradecane. Curves are fits with the population balance model.

Measurement of Aqueous Oil Concentration. Turbidity of the
diluted emulsion samples during solubilization was measured
periodically by using an UV-vis spectrophotometer (Model UV-
160A, Shimadzu Scientific Instruments, Pleasanton, CA) at a
wavelength of 800 nm. The measured turbidity was converted to oil
droplet concentration by using a calibration curve, and the aqueous
oil concentration could be found from a mass balance.
The calibration curves were prepared from emulsions with a range
of known initial oil droplet concentrations and droplet sizes,23,24 and
therefore, the relationship of turbidity to oil concentration as a function
of droplet size could be found. For experiments with sucrose,
calibration curves were prepared separately using surfactant solutions
with 30 wt % sucrose. The presence of sucrose reduced the refractive
index difference between the droplets and the continuous phase
significantly, which increased the error in these turbidity measure-
ments. In addition, we found that the presence of dodecane-containing
Tween 20 micelles appeared to affect somewhat the relationship
between turbidity and oil droplet concentration. For these reasons,
it was found to be more accurate to analyze the turbidity measurements
to yield a normalized aqueous oil concentration, derived by calculating
the fraction of oil lost from the droplets relative to the initial measured
oil droplet concentration. In this form, small errors in the calibration
relationship largely cancel out, and the result closely approximates
the amount of oil in the aqueous phase compared to the total oil in
the system. These results were used to confirm qualitatively the
trends seen with the light-scattering data.
Measurement of Oil Droplet Size Distribution. A light-scattering
particle size analyzer (S3500, Microtrac, Montgomeryville, PA),
with a tri-laser system of 780 nm wavelength and analysis based on
modified Mie scattering, was used to measure the size distribution
of emulsions. Refractive indices for n-hexadecane, n-tetradecane,
and n-dodecane are 1.43, 1.43, and 1.421, respectively, and values
for water and 30 wt % sucrose solutions are 1.333 and 1.381,
respectively. Appropriate aqueous solutions were used as reference.
(24) McClements, D. J.; Dungan, S. R. Colloids Surf. A: Physicochem. Eng.
Aspects 1995, 104, 127.
The surface mean diameter was calculated from ds ) ΣiVi/Σi(Vi/di),
where di is the midpoint of the size interval i and Vi is the volume
percent of particles in that interval.
Measurement of Saturation Oil Concentration (Cmiceq). Glass
vials of emulsions were prepared with different initial oil concentra-
tions suspended in aqueous solution with a fixed surfactant
concentration. These were kept in a water bath at 30 ( 1 °C for
n-hexadecane and n-tetradecane or at room temperature (22 ( 1 °C)
for n-dodecane. The decrease in oil turbidity over time in each vial
was measured by using a UV-vis spectrophotometer at a wavelength
of 800 nm. After ∼700 h for n-hexadecane, 120 h for n-tetradecane,
and 50 h for n-dodecane, the turbidity approached a constant value
as micellar solutions became saturated. The remaining turbidity from
the excess oil beyond the solubilization limit was plotted against the
prepared initial oil concentrations,25 and the saturation oil concentra-
tion was found from the x intercept. The details of this procedure
are described by Ariyaprakai and Dungan.21 In order to measure
saturation oil concentrations in sucrose solutions, emulsions with
different initial oil concentrations were kept in glass vials containing
30 wt % sucrose in aqueous surfactant solution.
Results
Figures 2-4 show data measured during solubilization of dilute
(∼0.04 wt %), nearly monodisperse alkane emulsions into 3 wt
% nonionic surfactant solutions. Measurements of the average
drop size (part a) and aqueous oil concentrations (part b) are
shown for solutions containing either 0 or 30 wt % sucrose. The
sucrose solution had a 3.2-fold larger viscosity than that of the
solution without sucrose. As shown in Figure 2, this enhanced
viscosity did not have a discernible effect on the solubilization
kinetics of n-hexadecane oil in the 3 wt % Tween 20 aqueous
solution. Data are presented from both light scattering and turbidity
measurements, and both support this same conclusion. However,
(25) Weiss, J.; McClements, D. J. Langmuir 2000, 16, 5879.
3064 Langmuir, Vol. 24, No. 7, 2008 Ariyaprakai and Dungan

Figure 4. Solubilization kinetics of nearly monodisperse dodecane-in-water emulsions as a function of time into 3 wt % Tween 20 micellar
solutions with and without sucrose. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial
concentration in emulsion. Initial emulsions contained 0.04 wt % dodecane. Curves are fits with the population balance model.

Figure 5. Solubilization kinetics of nearly monodisperse hexadecane-in-water emulsions as a function of time into 3 wt % SDS micellar
solutions with and without sucrose. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial
concentration in emulsion. Initial emulsions contained 0.04 wt % hexadecane. Curves are fits with the population balance model.

Figure 6. Solubilization kinetics of nearly monodisperse tetradecane-in-water emulsions as a function of time into 3 wt % SDS micellar
solutions with and without sucrose. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial
concentration in emulsion. Initial emulsions contained 0.04 wt % tetradecane. Curves are fits with the population balance model.

from Figures 3 and 4, the higher viscosity reduced the
solubilization rate of n-tetradecane and n-dodecane significantly.
The viscosity effect appears to influence the dodecane solubi-
lization most strongly.
Dungan et al.,16 in contrast, did not see a very strong influence
of viscosity on the rate of n-decane solubilization into 2 wt %
Tween 20 micellar solutions. This study examined polydisperse
emulsions, for which the decrease in droplet size could not be
monitored and therefore only turbidity data could be analyzed.
The turbidity decrease in these decane experiments was so rapid
that early-time data, which is most sensitive to the kinetic
mechanism, was not captured. This fact, coupled with the lower
sucrose concentrations used, may explain why an effect of
viscosity could not be clearly observed in our earlier study and
provided additional motivation for the present investigation.
The corresponding results for SDS micellar solutions are given
in Figures 5-7. Here, solubilization rates for all three chain
lengths were influenced by aqueous viscosity. However, on the
basis of the light-scattering data, hexadecane solubilization rates
seemed to exhibit a weaker dependence on sucrose’s presence
than did the shorter-chain oils.
Unfortunately, additives that increase the aqueous viscosity
will also tend to alter to some extent activities in the aqueous
solution. To account for such effects, we measured the equilibrium
oil concentrations Cmiceq in the micellar solutions in the presence
and absence of sucrose. The measured saturation oil concentra-
tions in 3 wt % surfactant solution with and without sucrose are
shown in Table 1. The saturation oil concentration in the micelles
was between 30% and 50% higher in the presence of 30 wt %
sucrose than in its absence for all oil types and for both Tween
20 and SDS.
Table 2 presents values of the mass transfer coefficients keff
for n-dodecane solubilized in 1-4 wt % Tween 20 and SDS
aqueous solutions. These values were obtained from fitting the
Solubilization of Monodisperse Emulsion Droplets Langmuir, Vol. 24, No. 7, 2008 3065

Figure 7. Solubilization kinetics of nearly monodisperse dodecane-in-water emulsions as a function of time into 3 wt % SDS micellar
solutions with and without sucrose. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial
concentration in emulsion. Initial emulsions contained 0.04 wt % dodecane. Curves are fits with the population balance model.
Table 1. Saturation Concentrations and Effective Mass Transfer Coefficients, keff (from Population Balance Analysis of Light
Scattering Results), of 0.04 wt % Oil Solubilized in 3 wt % Surfactant Solutions with 0 wt % or 30 wt % Sucrose
Tween 20 SDS
keff Cmiceq keff Cmiceq
(m/s) (kg/m3 ) (m/s) (kg/m3)
n-hexadecane 0 wt % sucrose 1.19 × 10-9 0.607 0.22 × 10-9 0.673
30 wt % sucrose 0.84 × 10-9 0.802 0.13 × 10-9 0.887
n-tetradecane 0 wt % sucrose 1.16 × 10-8 0.705 0.34 × 10-8 0.970
30 wt % sucrose 0.57 × 10-8 0.949 0.13 × 10-8 1.440
n-dodecane 0 wt % sucrose 0.96 × 10-7 0.759 0.26 × 10-7 1.296
30 wt % sucrose 0.29 × 10-7 1.065 0.10 × 10-7 1.870

Table 2. Saturation Concentration, Cmiceq, and Effective Mass The effect of salt addition on solubilization kinetics of
Transfer Coefficients, keff (from Population Balance Analysis of hexadecane into SDS micelles is displayed in Figure 10. As the
Light Scattering Results), of n-Dodecane Solubilization salt concentration increased from 0 to 300 mM, the solubilization
mass transfer rate of ∼0.04 wt % n-hexadecane in 3 wt % SDS aqueous solution
saturation oil coefficient keff was slightly increased.
wt % concentration (m/s) (light scattering
surfactant Cmiceq (kg/m3) data and eq 1)
Discussion
1% SDS 0.242 0.69×10-7
2% SDS 0.730 0.39×10-7 Effect of Sucrose Addition on Solubilization Rates. The
3% SDS 1.296 0.26×10-7 increase in Cmiceq upon addition of sucrose (Table 1) likely resulted
4% SDS 2.087 0.17×10-7 from effects of sucrose on the surfactant micelle properties.
1% Tw20 0.277 1.03×10-7 Acharya et al.26 found that, with added sucrose up to 0.5 M (∼17
2% Tw20 0.506 1.06×10-7
3% Tw20 0.759 1.00×10-7 wt %), the cmc of both Tween 20 and SDS decreased and the
4% Tw20 1.050 0.92×10-7 aggregation number of the micelles increased. Micellar growth
could create a larger capacity for solute, causing the increased
population balance to light-scattering data presented in Figures Cmiceq values we measured in the presence of sugar. Interestingly,
8a and 9a. As described by Ariyaprakai and Dungan,21 this balance higher Cmiceq values in the presence of sucrose would tend to
consists of tracking the decrease in droplet radius as drive a faster solubilization process, so that the effect of viscosity
on slowing solubilization kinetics may be even larger than is
dR(i) keff apparent in Figures 2-7. We decouple these effects of equilibrium
) (c - Cmiceq) (1) solubilization from the kinetics by using the population balance
dt Foil aq
described above (Table 1).
Here R(i) is the radius of the ith droplet, caq is the oil concentration The slower rates of solubilization for systems of higher
in aqueous solution at time t, and Foil is the density of the oil viscosity, shown especially in Figures 3-7 and Table 1, signal
solute. Values for R(i) and caq are obtained from our light-scattering a likely role of diffusion in the controlling mechanism for solute
measurements, combined with a mass balance on the amount of transfer. Previous studies within emulsions on the effect of initial
total oil in the system. Cmiceq was measured independently (Table droplet size, convection, or addition of polymers,16,21 as well as
2), and the oil density is given in Table 3. The corresponding studies on single, large drops,17,27 indicate that diffusion of
turbidity data are also presented in Figures 8 and 9 (part b). keff micelles does not play the dominant role. This means that, within
values for dodecane can be compared to those for n-hexadecane the pathway II mechanisms, viscosity should not have a major
and n-tetradecane already provided by Ariyaprakai and Dungan.21 influence on the rates. Thus, systems exhibiting a strong viscosity
For dodecane, keff with SDS micelles decreased with an increase dependence, in our view, are far more likely to be controlled by
of surfactant concentration from 1 to 4 wt %, as was the case pathway I than II. Further, these previous studies indicate that
for the other alkane solutes. However, the mass transfer the controlling mechanism cannot consist of a pure diffusion
coefficients for dodecane into Tween 20 solutions appeared mechanism but instead requires molecular diffusion coupled to
approximately constant. The mass transfer coefficients for Tween
(26) Acharya, K. R.; Bhattacharyya, S. C.; Moulik, S. P. J. Photochem.
20 in Table 2 are of the same order of magnitude as for SDS, Photobiol. A 1999, 122, 47.
but higher by a factor of ∼2-5. (27) Pena, A. A.; Miller, C. A. J. Colloid Interface Sci. 2001, 244, 154.
3066 Langmuir, Vol. 24, No. 7, 2008 Ariyaprakai and Dungan

Figure 8. Solubilization kinetics of nearly monodisperse dodecane-in-water emulsions as a function of time into Tween 20 micellar solutions
of various concentrations. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial concentration
in emulsion. Initial emulsions contained 0.04 wt % dodecane. Curves are fits with the population balance model.

Figure 9. Solubilization kinetics of nearly monodisperse dodecane-in-water emulsions as a function of time into SDS micellar solutions
of various concentrations. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to initial concentration
in emulsion. Initial emulsions contained 0.04 wt % dodecane. Curves are fits with the population balance model.
Table 3. Physical Properties of Alkane Solutes and Surfactants Used in Experiments
parameter n-hexadecane n-tetradecane n-dodecane
chemical structure C16H34 C14H30 C12H26
molecular weight (g/mol) 226.4 198.4 170.3
oil density (kg/m3) 773 763 750
specific molar volume (m3/mol) 2.93×10-4 2.60×10-4 2.27×10-4
aqueous solubility, Cweq (kg/m3)a 9.6×10-9 4.22×10-7 3.5×10-6
diffusion coefficient in water, 5.9×10-10 6.4×10-10 5.6×10-10
Dw (m2/s)b
diffusion coefficient in 30 wt % 2.3×10-10 2.5×10-10 2.1×10-10
sucrose aqueous solution,
Dw (m2/s)b
parameter Tween 20 SDS
chemical structure C58H114O26 CH3(CH2)11OSO3Na
molecular weight (g/mol) 1227.5 288.4
cmc (wt %) 0.0061 0.24
micelle radius (nm) 3.2 2.2
micelle aggregation number 86 50
a
From Taylor.28 b
Calculated from the Wilke-Chang equation at 30 °C for hexadecane and tetradecane and at 22 °C for dodecane.

a fast and irreversible solute uptake reaction step. The early time
flux, J, in this case can be represented by16
J ) Cweq xkr+Dwφmic
where Cweq is the aqueous solubility of the oil solute, kr+ (s-1)
is the rate constant of uptake of oil molecules from water into
the micelles, and φmic is the volume fraction of micelles in aqueous
solution (i.e., the micelle concentration.) Equation 2 predicts an
inverse dependence of flux on viscosity µ through the contribution
of Dw, the diffusion coefficient of the oil molecule in aqueous
solution. The Stokes-Einstein or Wilke-Chang equation predicts
that Dw ∼ µ-1, a prediction confirmed experimentally for sucrose
solutions.20 The resulting dependence of flux on µ-1/2 likely
accounts for the strong effect of sucrose addition on the
solubilization kinetics exhibited in Figures 3-7.
Effects of Viscosity and Solute Chain Length. A decrease
(2) in the alkane chain length from 16 to 12 is associated with a
decrease in solute size, an increase in solute diffusion coefficient,
and an increase in solute solubility in water. Estimated values
for these properties are given in Table 3. For systems controlled
by pathway I, eq 2 predicts a linear dependence of solubilization
rate on Cweq. The values for solubility presented in Table 3,
which are taken from Taylor,28 indicate that the solubility in
water drops by more than 2 orders of magnitude as we go from
dodecane to hexadecane and that this effect explains the substantial
(28) Taylor, P. AdV. Colloid Interface Sci. 2003, 106, 261.
Solubilization of Monodisperse Emulsion Droplets
Figure 10. Solubilization kinetics of nearly monodisperse hexadecane-in-water emulsions as a function of time into 3 wt % SDS micellar
solutions with various concentrations of NaCl. Data represent (a) surface mean diameter (ds) and (b) aqueous oil concentration relative to
initial concentration in emulsion. Initial emulsions contained 0.04 wt % hexadecane.
slowing of the solubilization kinetics as the chain length increases
(Figures 2-7). It is important to note, however, that controversy
remains over the magnitude of solubility values for very long
chain alkanes,21,28-30 with some researchers reporting much higher
values than those given in Table 3.
Our comparison is given a more quantitative basis by using
the population balance model (eq 1) to extract effective mass
transfer coefficients from our light-scattering data for dodecane.
These values are given in Table 2 and can be compared with
values given in our previous paper for tetradecane and hexadecane.
For these three solutes in solutions of either SDS or Tween 20
micelles, the mass-transfer coefficient dropped by a factor of 10
as we increased the chain length by two carbons.
The strong dependence of solubilization kinetics on the length
of the oil solute chain proved to be important in interpreting our
viscosity results in Figures 2-7. The strong dependence on
viscosity for the shorter-chain alkanes like n-dodecane and
n-tetradecane were consistent with the molecular diffusion
pathway described in eq 2, where oil must diffuse in molecular
form out into the water first, before being picked up by micelles.
For hexadecane with its very low water solubility, this molecular
diffusion pathway may become so inefficient that it allows
pathway II to start to contribute substantially to the solubilization
process. The result is a reduction in the influence of viscosity
on the solubilization kinetics for solutes of increased chain length,
especially for the Tween 20 system.
If in surfactant solutions with either 0 or 30 wt % sucrose, we
assume that φmic and Cweq in eq 2 are approximately constant and
that kr+ is also proportional to the diffusion coefficient of the oil
molecule;15 eq 2 predicts that the flux in the solution without
sucrose should be larger by a factor of 2.6 than that in the 30
wt % sucrose surfactant solution. Using the extracted mass transfer
coefficients, keff, obtained from fitting light-scattering results to
the population balance and our measured saturated oil concen-
trations Cmiceq (see Table 1), the ratio of fluxes in the low- and
high-viscosity systems can be determined experimentally. We
find that, for n-hexadecane, n-tetradecane, and n-dodecane solutes,
this ratio is 1.1, 1.5, and 2.4, respectively, for Tween 20 micelles.
For SDS micellar solubilization, the ratios are 1.3 (C16), 1.8
(C14), and 1.8 (C12). The obtained values are closer to the
predicted factor of 2.6 for the shorter alkanes, as expected on
the basis of the above analysis.
It should be noted that there is likely to be some effect of
sucrose addition upon the solubility of alkanes in water, most
(29) Coates, M.; Connell, D. W.; Barron, D. M. EnViron. Sci. Technol. 1985,
19, 628.
(30) Shaw, D. G.; Maczynski, A.; Goral, M.; Wisniewska-Goclowska, B.;
Skrzecz, A.; Owczarek, I.; Blazej, K.; Haulait-Pirson, M. C.; Hefter, G. T.; Kapuku,
F.; Maczynska, Z.; Szafranski, A. J. Phys. Chem. Ref. Data 2006, 35, 687.
Langmuir, Vol. 24, No. 7, 2008 3067
likely leading to a small reduction in solubility. Such a reduction
could contribute to the small increase in micellar saturation
concentrations for the solutes in sucrose solution reported in
Table 1. Unfortunately, literature values for the aqueous solubility
of alkanes in the presence of sucrose are not available. However,
a recent solubility study of flavor compounds in water and in
sucrose solution31 showed that, for the most hydrophobic flavor
(ethyl hexanoate), solubility in a 30% sucrose solution was
reduced about 25% relative to that in water alone and that the
effect of sucrose was weaker for the more nonpolar solutes. This
result would suggest that any impact of sucrose on alkane
solubility should be small. Furthermore, such an effect would
act only within the molecular pathway mechanism, where it would
slightly augment the influence of sucrose on the kinetics. Thus,
such a contribution should not alter substantially our mechanistic
comparisons above.
Surfactant Concentration Dependence. Several researchers
have noted that in a pathway I mechanism, the solubilization
flux should increase as the square root of the micelle
concentration.15-17,21 This dependence is shown in eq 2. In Figure
11 is presented the solubilization flux, J, plotted as a function
of φ1/2 for each alkane and for both surfactants. Micelle volume
fractions were determined using the parameters in Table 3. A
reasonable linear correlation between J and φ1/2 generally exists,
although we note that other scalings of J on micelle concentration
would also work. By comparing the slopes in Figure 11 with the
predictions of eq 2, we may extract the rate constant kr+ for the
micelle uptake reaction. The obtained values for kr+ for Tween
20 micelles are 1.0 × 109 s-1 for n-hexadecane, 5.2 × 107 s-1
for n-tetradecane, and 7.8 × 107 s-1 for n-dodecane. For SDS
micelles, this comparison yielded 4.2 × 106 s-1 for n-tetradecane
and 6.4 × 106 s-1 for n-dodecane. The latter rate constants
measured for tetradecane or dodecane solubilization are quite
close to the value measured by Todorov et al.,17 using single
large decane droplets transferring into SDS micelles.
The uptake rate constants for Tween 20 micelles are at least
an order of magnitude higher than for SDS, and kr+ for
n-hexadecane solubilized in Tween 20 solutions is more than an
order of magnitude higher than for the other oils. We believe this
latter observation is an indirect reflection of a contribution from
the pathway II mechanism, as discussed above. Because pathway
II here enhances the solubilization rate, ignoring its contribution
results in an inflated value for kr+. For the case of n-hexadecane
solubilized in SDS micellar solutions, the data for J did not show
a clear linear dependence on the square root of the micelle
concentration.
(31) Covarrubias-Cervantes, M.; Bongard, S.; Champion, D.; Voilley, A.
FlaVour Fragr. J. 2005, 20, 265.
3068 Langmuir, Vol. 24, No. 7, 2008
Figure 11. Values for solubilization flux, keffCmiceq. keff obtained from fits of light scattering measurements (symbols) or calculated
(s, ---) using predictions of kr+ from Kabalnov and Weers.15 SDS (9, s) or Tween 20 (b, ---) used with (a) hexadecane, (b) tetradecane,
or (c) dodecane emulsions.
We can compare these experimentally determined uptake rate
constants with theoretical estimates based on diffusion control
at the surface of the micelle, as discussed by Kabalnov and
Weers.15 This estimate assumes that once solute reaches the
micelle itself, it is taken up at an infinitely fast rate relative to
its diffusion time through the region surrounding the micelle, so
that
kr+ ) 3Dw/Rmic2 (3)
From this estimate for kr+, the overall solubilization flux can be
calculated from eq 2. These theoretically predicted rates are plotted
in Figure 11 and compared with the results measured from this
study. For all alkanes and both surfactants, the rates obtained
from the experiments were found to be much slower than from
the theoretical estimate, with the exception of n-hexadecane
solubilized in Tween 20. This general trend may indicate that
the uptake rate kr+ is actually much smaller than the calculated
value from eq 3, and therefore, the diffusion-controlled assumption
for micelle uptake does not hold. In particular, we note that the
faster solubilization fluxes for the Tween 20 systems indicate a
larger value of kr+ than for the SDS systems. A diffusion-
controlled reaction at the surface of the micelle, however, depends
inversely on square of the micelle radius and, thus, predicts slower
micelle uptake reactions for the larger Tween 20 micelles (see
Table 3). Neogi32 proposed in his theoretical study that the energy
barrier encountered by the solute as it tries to enter the micelle
may be significant. Such an energy barrier would reduce kr+
below the diffusion-controlled limit.
Alternatively, we can explain the differences between diffusion-
controlled theory and experiment in Figure 11 by positing the
presence of an additional interfacial resistance (1/ki) within
pathway I, associated with transferring individual oil molecules
across the emulsion drop interface and into the water. Todorov
(32) Neogi, P. J. Colloid Interface Sci. 2003, 261, 542.
Ariyaprakai and Dungan
and co-workers indicated the presence of such a resistance in
their measurements of decane transfer from single large drops
into SDS micellar solutions.17 This step is illustrated in Figure
1 and is described theoretically by eq 25 of Dungan et al.16 By
inverting the latter equation, we see that the interfacial resistance
can be calculated by subtracting the bulk transport resistance
(Cmiceq/Cweq xDwkr+φmic), determined theoretically as in Figure
11, from the total measured resistance (1/keff) found from our
experiments. However, for the SDS system in particular, the
interfacial resistance (1/ki) obtained in this fashion was found to
be an order of magnitude larger than that from the resistance for
transferring the oil molecule through the bulk phase. This would
imply that bulk diffusion steps make a negligible contribution
to the overall mechanism, which would contradict the strong
viscosity dependence we observed in our data. The putative values
for ki we calculate for both types of surfactants, furthermore,
display a substantial dependence on overall surfactant concentra-
tion, which seems implausible this far above the cmc. Therefore,
although the interfacial resistance may make some contribution,
such an effect is likely to be combined with a rate constant, kr+,
of oil solute uptake that is lower than predicted for diffusion
control around the micelle.
Flux of hexadecane into Tween 20 micelles, on the other hand,
proceeds more rapidly than predicted by a molecular pathway
with reaction-enhanced diffusion, as calculated theoretically by
eqs 2 and 3. Here reaction-enhanced diffusion is no longer a
likely dominant mechanism, consistent with the weak dependence
on viscosity that we observed with this system. The interfacially
driven pathway II instead appears controlling for this case.
The results in Figure 11 for hexadecane and the accompanying
shift in mechanism also seem to signal a change in the relation
between flux and nonionic surfactant concentration. We showed
previously that keff values for hexadecane solubilization in Tween
20 solutions are independent of surfactant concentration over
the range studied.21 Consequently, it is expected that J ∼ φmic
Solubilization of Monodisperse Emulsion Droplets
for this case, yielding the stronger dependence of flux on surfactant
concentration displayed in Figure 11.
Role of Electrostatic Interaction for Ionic Surfactants. For
solutes with 12 or 14 carbons solubilized within SDS micelles,
there seems a clear contribution from a pathway I mechanism,
in particular steps controlled by reaction-enhanced diffusion.
However, for hexadecane solubilization in SDS, the evidence
from our experiments is more ambiguous. A reduced dependence
on viscosity was observed by light scattering measurements but
was not obvious in the turbidity measurements. Furthermore,
there was no clear direct relationship between flux and the square
root of the micelle concentration in Figure 11. We decided to
explore whether there could be contributions also from pathway
II by testing the effect of salt concentration on solubilization
kinetics in this system. Pathway II involves transfer of oil directly
into a micelle at the emulsion interface, and it has been
proposed6,7,9,12 that this path may be controlled by collision of
micelles with the interface, dissolution of micelles prior to
adsorption, or budding of micelles off from the droplet interface.
For anionic surfactants with their charged micelle and emulsion
surfaces, it would be expected that these mechanisms would
show a strong dependence on salt concentration, as salt screens
electrostatic repulsion or alters interfacial curvature energies.
However, Figure 10 shows only a weak enhancement in
solubilization rate in the presence of 100 or 300 mM NaCl
compared to the no-salt case. Such a weak effect would be
consistent with the molecular transfer steps associated with
pathway I but would not seem to support a role for micelle
collision or growth at the emulsion interface. Furthermore, from
Figure 10 we see no indication that reduction of the Debye length
through addition of salt is sufficient to reduce electrostatic
repulsive barriers and thus to shift the solubilization mechanism
toward pathway II.
The small effect of salt seen in Figure 10 could be attributed
to other effects of NaCl on SDS properties. Addition of salt
should increase the micelle radius and solubilization capacity,33
which would in turn enhance the solubilization rate. Oil solubility
in molecular form in the aqueous solution would be probably be
decreased in the presence of salt, which would tend to counteract
the former trend. Interactions between individual molecules of
solute and surfactant at the emulsion interface and at the micelle
surface might also be affected. These contributions, which are
associated with steps in the molecular pathway I mechanism,
apparently lead to an effect, albeit small, of NaCl on the
solubilization kinetics.
Conclusions: Summary of Mechanisms
Our results allow us to evaluate the two mechanistic pathways
illustrated in Figure 1 in terms of their dependence on the aqueous
viscosity, surfactant concentration, and the addition of salt. Since
viscosity has a strong influence on solubilization rate, especially
for the shorter alkanes, n-dodecane and n-tetradecane, a molecular
pathway I is proposed as a dominant contributing mechanism.
For the longer chain-length alkane, n-hexadecane, a weaker
dependence on viscosity was generally observed, particularly
(33) van Os, N. M.; Haak, J. R.; Rupert, L. A. M. In Physico-Chemical Properties
of Selected Anionic, Cationic and Nonionic Surfactants; Elsevier: Amsterdam,
1993; p 34.
Langmuir, Vol. 24, No. 7, 2008 3069
within Tween 20 micelles. This strongly suggests that both
pathways I and II can contribute, at least for nonionic micelles.
In contrast to pathway I, which depends importantly on molecular
diffusion through the bulk solvent, pathway II is an interfacially
dominated mechanism. In Tween 20 micelles, we thus believe
we observed mixed kinetics, in which parallel diffusive and
interfacial steps occurred. The competition between the two
mechanisms depended on which pathway was more efficient.16
The magnitude of the viscosity effect in Figure 4 for n-dodecane
was the largest, as a consequence of the relatively high aqueous
oil solubility of this solute, thus allowing a greater contribution
from molecular diffusion through the water. As the solute chain
length was increased to 14 and then to 16, there was a major
reduction in aqueous solubility, making the molecular pathway
less efficient. This allowed the interfacial pathway II to begin
to contribute. For n-hexadecane, where viscosity had very little
influence on the solubilization kinetics, we believe that direct
transfer of solute into the micelles at the interface began to
dominate the overall kinetics. The dominance of the interfacial
mechanism for hexadecane can also account for the relatively
high values of the flux of solute into Tween 20 micelles, compared
to predictions from pathway I theories (Figure 11). The
contributions of a second, parallel mechanism is also able to
explain the higher “apparent” solute uptake rate constant found
for Tween 20 micelles compared to SDS.
For anionic SDS, the molecular pathway I is proposed as the
main pathway for the solubilization process, in agreement with
earlier researchers. From Figures 6 and 7, the extent of the effect
of viscosity on the solubilization rate was observed to be very
similar for tetradecane and dodecane. A significant effect of
viscosity on n-hexadecane solubilization in Figure 5 indicates
that a molecular diffusive pathway was important here as well,
but interfacial mechanisms may also have been playing a role.
The weak effect of salt in this system and the slow flux rate in
Figure 11 compared to theory suggests that this interfacial step
was likely molecular in nature and not associated with collision,
dissolution, or formation of micelles at the emulsion interface.
For both anionic and nonionic micelles, the solute uptake rate
appeared to be lower than that predicted by diffusion control at
the micelle surface.
The strong correlation of rate with alkane chain length
confirmed that viscosity retarded the movement of individual oil
molecules, rather than surfactant micelles or monomers. For the
case of the pathway II dominant mechanism (n-hexadecane in
Tween 20 solutions), the rate-limiting step must be one relatively
unaffected by the aqueous viscosity. For micelle adsorption/
desorption steps that depend on bulk diffusion of micelles, a
viscosity increase would also retard the solubilization rate. Thus,
these steps are not controlling within pathway II mechanisms,
leaving other possibilities, such as a surface barrier to adsorp-
tion14,34 or the “budding” of micelles from the interface, as
potential rate-limiting steps in transferring hexadecane and other
very long chain solutes.
LA703204C
(34) Todorov, P. D.; Marinov, G. S.; Kralchevsky, P. A.; Denkov, N. D.;
Durbut, P.; Broze, G.; Mehreteab, A. Langmuir 2002, 18, 7896.