10086 Langmuir 2002, 18, 10086-10090

Ostwald Ripening of Alkane in Water Emulsions Stabilized

by Sodium Dodecyl Benzene Sulfonate
Thi Kieu Nguyen Hoang,†,‡ Van Binh La,‡ Luc Deriemaeker,† and Robert Finsy*,†
Department of Physical and Colloid Chemistry, Vrije Universiteit Brussel, Pleinlaan 2,
B-1050 Brussels, Belgium, and the Faculty of Chemical Technology, Hanoi University of
Technology, Hanoi, Vietnam

Received May 15, 2002. In Final Form: September 2, 2002

The Ostwald ripening of alkane in water emulsions stabilized by the anionic surfactant sodium dodecyl
benzene sulfonate (SDBS) was investigated. For emulsions prepared under high-shear conditions in a
microfluidizer, ripening rates do not depend on the micellar surfactant concentration. The aging process
is due to the molecular transport of alkane through the continuous phase, and there is no significant
contribution from a transport mechanism by the micelles. When micellar surfactant solutions are added
to an already formed emulsion, the Ostwald ripening process is not affected, confirming the fact that the
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micelles do not contribute to the transport of alkane molecules.

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1. Introduction In eq 2, Vm stands for the molar volume of the dispersed

The physical degradation of emulsions is due to the
spontaneous trend toward a minimal interfacial area
between the dispersed phase and the dispersion medium.
Minimizing the interfacial area is mainly achieved by two
mechanisms: first, coagulation possibly followed by
coalescence and second, Ostwald ripening (OR). The
former is the most studied (see, for example, ref 1).
However, if properly stabilized against the coagulation/
coalescence process, the latter can cause a substantial
breakdown of the emulsion.
Ostwald ripening is the process by which larger particles
(or, for emulsions, droplets) grow at the expense of smaller
ones because of the higher solubility of the smaller
particles (Gibbs-Thomson or Kelvin effect) and molecular
diffusion through the continuous phase.
A theoretical description of Ostwald ripening in two-
phase systems has been developed independently by
Lifshitz and Slyozov and by Wagner (LSW theory).2-5 One
of their major results is that in the long time limit a
stationary regime is reached for which the ripening rate
v is given by
da3N 4
v) ) RDmC(∞) (1)
dt 9
In eq 1, aN denotes the number-average particle radius,
and Dm is the dispersed-phase molecular diffusion coef-
ficient; R is a material-dependent constant called the
capillary length, defined by
2γVm
R) (2)
RT
* To whom correspondence should be sent. E-mail: Robert.Finsy@
vub.ac.be. Tel: +32-2-629-3485. Fax: +32-2-629-3320.
† Vrije Universiteit Brussel.
‡ Hanoi University of Technology.
(1) Tadros, T.; Vincent, B. In Encyclopedia of Emulsion Technology;
Becher P., Ed.; Marcel Dekker: New York 1983; p 131.
(2) Lifshitz, I. M.; Slyozov, V. V. J. Phys. Chem. Solids 1961, 19, 35.
(3) Wagner, C. Z. Elektrochem. 1961, 65, 581.
(4) Kabalnov, A. S.; Shchukin, E. D. Adv. Colloid Interface Sci. 1992,
38, 69.
(5) Taylor, P. Adv. Colloid Interface Sci. 1998, 75, 107.
phase, γ is the interfacial tension, and R and T have their
usual meanings of gas constant and absolute temperature.
This result predicts that the aging or average droplet-size
increase is mainly determined by the bulk solubility C(∞)
of the dispersed phase in the continuous one. This feature
of Ostwald ripening has been verified in several experi-
mental studies6-20 of alkane in water emulsions stabilized
against coagulation by surfactants.
If added in sufficiently large amounts and after complete
coverage of the oil-water interface, surfactants sponta-
neously form micelles in the continuous aqueous phase.
The presence of micelles drastically increases the solubility
of the oil. Therefore, an effect of micelles on the Ostwald
ripening may be anticipated. It might be simplistically
expected that replacing the bulk oil solubility C(∞) in eq
1 by the concentration of oil solubilized by the micelles
and using the micellar diffusion coefficient instead of the
molecular one would yield the Ostwald ripening rate in
the presence of micelles. This approach predicts an
increase in the rates by a factor of about 200 to 1000.5
(6) Kabalnov, A. S.; Markarov, K. N.; Pertzov, A. V.; Shchukin, E.
D. J. Colloid Interface Sci. 1990, 138, 98.
(7) Kabalnov, A. S. Langmuir 1994, 10, 680.
(8) Taylor, P. Colloids Surf., A 1995, 99, 175.
(9) Soma, J.; Papadopoulos, K. D. J. Colloid Interface Sci. 1996, 181,
225.
(10) Bremer, L.; De Nijs, B.; Deriemaeker, L.; Finsy, R.; Geladé, E.;
Joosten, J. Part. Part. Syst. Charact. 1996, 13, 350.
(11) De Smet, Y.; Malfait, J.; De Vos, C.; Deriemaeker, L.; Finsy, R.
Bull. Soc. Chim. Belg. 1996, 105, 789.
(12) De Smet, Y.; Malfait, J.; DeVos, C.; Deriemaeker, L.; Finsy, R.
Prog. Colloid Polym. Sci. 1997, 105, 252.
(13) De Smet, Y.; Deriemaeker, L.; Finsy, R. Langmuir 1999, 15,
6745.
(14) Binks, B. P.; Clint, J. H.; Fletcher, P. D. I.; Rippon, S.; Lubetkin,
S. D.; Mulqueen, P. J. Langmuir 1999, 15, 4495.
(15) Weiss, J.; Herrmann, N.; McClements, D. J. Langmuir 1999,
15, 6652
(16) Weiss, J.; Cancelier, C.; McClements, D. J. Langmuir 2000, 16,
6833
(17) Hoang, T. K. N.; La, V. B.; Deriemaeker, L.; Finsy, R. Langmuir
2001, 17, 5166.
(18) Hoang, T. K. N.; La, V. B.; Deriemaeker, L.; Finsy, R. Langmuir
2002, 18, 1485.
(19) De Smet, Y.; Deriemaeker, L.; Parloo, E.; Finsy, R. Langmuir
1999, 15, 2327.
(20) De Smet, Y.; Danino, D.; Deriemaeker, L.; Talmon, Y.; Finsy, R.
Langmuir 2000, 16, 961.

10.1021/la0204545 CCC: $22.00 © 2002 American Chemical Society

Published on Web 11/15/2002
Ostwald Ripening of an Alkane in H2O Emulsions
Experimental studies report hardly any increase. Several,
sometimes conflicting, results and explanations are
given.6-20
Some authors8,9 observe ripening rates that increase
with increasing surfactant concentration above the critical
micellar concentration (CMC), which is with an increasing
number of micelles. The ripening rates relating to the
rates at low surfactant concentration (below or at about
the CMC) increase in both studies by a factor of 2 to 3.
However, Kabalnov7 did not observe any significant
increase with increasing surfactant (micellar) concentra-
tion above the CMC, and Desmet et al.13 observed even
a slight decrease. In these studies, anionic surfactants
(sodium dodecyl sulfate, SDS, and sodium dodecyl benzene
sulfonate, SDBS) were used. Since electrostatic repulsive
interactions are important in such systems, it may well
be that the observations and conclusions of these studies
do not apply to systems with nonionic surfactants.
Recently, some authors14-16 reported that in the presence
of nonionic surfactant micelles the ripening rate is 100-
to 1000-fold larger than the Ostwald ripening rates
predicted by eq 1. In a previous study,17 the ripening rates
of undecane and decane in water emulsions stabilized by
poly(ethylene glycol) monolaurate (PEM), a nonionic
surfactant, were determined at several surfactant con-
centrations. Surprisingly the measured ripening rates
were significantly below the rate that can be predicted by
the LSW theory and decreased in the presence of sur-
factant micelles.
In the study of Weiss et al.,16 it is mentioned that
although the observed ripening rates are a factor 30 to
130 larger than the ones predicted by eq 1, only a 4-fold
increase between the lowest and the highest rates was
measured. This ratio between the lowest and the highest
rates was also obtained in a previous study18 of the aging
of undecane and decane in water emulsions stabilized by
the same surfactant (Tween 20) used in the work of Weiss
et al.16 However, the Ostwald ripening rate enhancements
with surfactant concentrations over the theoretical pre-
dictions of the LSW theory are less than a factor 3.
Nevertheless, when micellar surfactant solutions were
added to already formed emulsions, increases in ripening
rates by a factor up to 20 were observed. This enhancement
is attributed to the perturbation of a quasi-equilibrium
distribution of the alkanes between the micelles and the
larger emulsion droplets in the already-formed emulsions.
The question that arose then was to what extent the
addition of an anionic surfactant would disturb the
Ostwald ripening process. This is investigated in the
present study of the ripening of decane, undecane, and
dodecane in water emulsions stabilized by sodium dodecyl
benzene sulfonate (SDBS).
2. Experimental Section
2.1. Material and Emulsion Preparation. Several emul-
sions of alkanes in water stabilized by the surfactant SDBS (tech.,
Aldrich, purity 96%) were prepared. The alkanes used were
dodecane, undecane, and decane (Aldrich, purity 99+%).
The first preparation method was the following. The oil
component was added to the aqueous surfactant solution. After
10 min of premixing with an Ultra-Turrax T25 with a rotor S25-
186, the coarse emulsion was further homogenized under high-
shear conditions for 10 min using a Y-110 microfluidizer. In this
way, emulsions with an oil (alkane) volume fraction of 0.01 and
surfactant concentrations in the range of 1.5 × 10-2 to 1.0 × 10-1
M were prepared.
In the second method, mother emulsions with an alkane volume
fraction of 0.005 and a surfactant concentration of 2 × 10-2 M
were prepared according to the previous procedure. To 2-mL
Langmuir, Vol. 18, No. 26, 2002 10087
Figure 1. Particle radius a as a function of undecane
concentration added to a 0.1 M SDBS solution.
samples of this mother emulsions, 1 mL of a surfactant solution
with a concentration in the range of 1 × 10-2 to 1.5 × 10-1 M was
added. Just before addition, the surfactant solutions were
homogenized for 5 min with the microfluidizer.
2.2. Particle-Size Measurement. Droplet sizes were deter-
mined with dynamic light scattering (DLS). The experimental
setup consists of an Ar+ laser (wavelength λ ) 488 nm), a
thermostated sample holder allowing us to control the temper-
ature (within (1 °C), and a photomultiplier (EMI 9863A) mounted
at a detection angle of 90°. The signal of the photomultiplier was
fed to a Brookhaven BI9000 correlator.
The measurement temperature was 25 °C. Just before each
particle-size measurement, a sample was prepared by diluting
the emulsion about 1000 times with distilled water to rule out
interactions and multiple scattering effects. In a previous study,12
it was shown that this measuring procedure did not affect the
droplet size.
Intensity-averaged radii were computed from the intensity
autocorrelation data with the cumulants method.21
2.3. Characteristics of the Surfactant SDBS: Critical
Micellar Concentration (CMC) and Specific Surface Area
(As). These were determined in a previous study.13 The CMC
was 5.0 × 10-3 M, and the specific area of the air-water interface
was 0.62 nm2.
2.4. Determination of the Alkane Solubility in Micellar
Surfactant Solutions. The amount of alkane that can be
solubilized by micellar surfactant solutions is determined as
follows. As long as the alkane is solubilized by the micelles, the
particle size that can be determined of such a solution is about
the micellar size (typically about 10 nm in diameter). When the
micelles are saturated by alkane, the remaining alkane is
dispersed in the form of larger droplets. Hence, beyond the
maximum solubilization, an increase in the particle size with
the amount of added alkane is to be expected.
The experimental procedure consisted of the addition of several
portions of alkane to typically 300 mL of a 0.1 M surfactant
solution. The solutions to which the alkane was added were
homogenized with the Ultra-Turrax and the microfluidizer as
explained in section 2.1. The homogenizer was used to speed up
the solubilization and to perform this study under the same
conditions as those used for the preparation of the emulsions
with an excess of surfactant micelles.
As an example, the particle size as a function of the amount
of undecane added to a 0.1 M SDBS solution is shown in Figure
1. Clearly, two regimes can be distinguished. In the first, the
particle size hardly increases with alkane concentration, whereas
in the second, the particle size increases linearly with alkane
concentration. The concentration at which linear fits to the two
regimes intersect is taken as the concentration of maximum
solubilization.
In this way, the solubility of undecane in 0.1 M SDBS, SDS,
and Tween 20 solutions was determined to be 1.9 × 10-3, 2.7 ×
10-3, and 3.5 × 10-3 mL of alkane in 1 mL of surfactant solution,
respectively. The solubility in 0.1 M SDS is in good agreement
with the value of 2.5 × 10-3 mL/mL reported in reference 7. The
solubilities of decane and dodecane in 0.1 M SDBS were
respectively 2.5 × 10-3 and 1.4 × 10-3 mL/mL.
10088 Langmuir, Vol. 18, No. 26, 2002
Table 1. Ostwald Ripening (OR) Rates as a Function of Surfactant Concentration for Several Undecane Emulsions
Prepared under High-Shear Conditions
SDBS
concentration
SDBS needed to cover
initial radius concentration the initial oil/water
emulsion a0 (nm) (M) interface
UA1 37 1.5 × 10-2 2.3 × 10-3
UA2 35 2.5 × 10-2 2.5 × 10-3
UA3 34 5.0 × 10-2 2.5 × 10-3
UA4 30 7.5 × 10-2 2.8 × 10-3
UA5 27 1.0 × 10-1 3.1 × 10-3
Figure 2. Evolution of a3 with time for an undecane emulsion
(top) and a dodecane emulsion.
3. Results and Discussion
3.1. Ostwald Ripening or Coalescence? In the first
series of experiments, it was investigated whether the
increase in particle size could be ascribed to Ostwald
ripening or to coalescence. The Ostwald ripening rate is
proportional to the solubility of the alkane (the factor C(∞)
in eq 1). Since the solubilities of alkanes in water vary
significantly with the alkane chain length, a considerable
variation of the ripening rate is to be expected on changing
the alkane chain length. However, the coalescence rate
depends, for a given system, on the initial particle size
and concentration. Hence, changing only the alkane chain
length would not alter the coalescence rate.
In Figure 2, the cube of the droplet radius a is plotted
as a function of time for the undecane and dodecane mother
emulsions. The surfactant (SDBS) concentration was 2 ×
10-2 M for both emulsions; the alkane volume fraction
was 0.005. In all of the experiments, no visible traces of
creaming or flocculation were observed during the moni-
toring of the ripening process by DLS.
Clearly replacing undecane by dodecane reduces the
ripening rates. Assuming a linear increase of a3 with time,
the ripening rates were estimated from the slope of the
linear fits. The ratio of 3.7 of these rates is in good
agreement with the ratio of 3.8 for the bulk solubilities
of the two alkanes (2.0 × 10-8 mL of undecane and 5.2 ×
10-9 mL of dodecane in 1 mL of water6). In a similar way,
a ratio of 4.4 for the ripening rates of decane to undecane
emulsions was found to be in fair agreement with the
ratio of 3.55 of the solubilities (7.1 × 10-8 mL of decane
in 1 mL of water6). Therefore, the main aging process is
Ostwald ripening and not coalescence. This implies that
the main aging mechanism results from the transport of
the alkane by molecular diffusion through the continuous
water phase. The somewhat higher ratio of ripening rates
of the decane to undecane emulsions might be attributed
to the fact that the decane emulsions are (a little) less
well stabilized against aging mechanisms different from
Ostwald ripening than the undecane emulsions. This has
already been observed in a previous study with the
surfactant Tween 20.18
Nguyen Hoang et al.
SDBS
concentration experimental rate
in the continuous aging rate enhancement
phase (M) (nm3/s) factor
1.3 × 10-2 7.53 1.15
2.2 × 10-2 9.52 1.46
4.7 × 10-2 9.56 1.46
7.2 × 10-2 8.01 1.23
9.7 × 10-2 8.23 1.26
Figure 3. Evolution of a3 with time for the undecane emulsions
(UA1 bottom to UA5 top) with increasing surfactant concentra-
tion and prepared under high-shear conditions. For clarity, the
different series have been translated along the ordinate over
2 × 105 nm3.
3.2. Ostwald Ripening as a Function of Surfactant
Concentration. To investigate the effect of an increasing
number of surfactant (SDBS) micelles, ripening experi-
ments were carried out as a function of the surfactant
concentration. In the first step, five undecane emulsions
all with a volume fraction of 0.01 but with different SDBS
concentrations in the range of 1.5 × 10-2 to 1.0 × 10-1 M
were prepared in the first way as described in section 2.1.
The surfactant concentrations and initial particle sizes
are reported in Table 1. The number of moles ns of
surfactant needed to cover the initial water/oil interface
was estimated by the procedure explained in section 4.2.1
of ref 13. In this procedure, the total interfacial area is
estimated from a model (log-normal) droplet size dis-
tribution. This leads to surfactant concentrations for
complete coverage in the range of 2.3 × 10-3 to 3.1 × 10-3
M (Table 1). Assuming that the first action of the surfactant
is to cover the oil-water interface, the initial surfactant
concentrations in the continuous phase are for all emul-
sions above the CMC.
The results of the monitoring of the droplet size as a
function of time are displayed in Figure 3 and Table 1.
The experimental Ostwald ripening rates were deter-
mined following the procedure explained in ref 19. This
procedure accounts for the initial nonstationary growth
regime.20. Thereby, the time evolution of a model of the
droplet size distribution is computed during the ripening
process.22 At every step of the ripening, the intensity and
number-weighted droplet sizes are computed from the
actual size distribution. With such tables of corresponding
intensity and number averages, the intensity-weighted
average sizes determined experimentally by DLS are
converted into number-average sizes. It is assumed that
during the ripening process the interfacial tension remains
constant. The ratio of the experimental rates to the ones
(21) Koppel, D. J. Chem. Phys. 1972, 57, 4814.
(22) De Smet, Y.; Deriemaeker, L.; Finsy, R. Langmuir 1997, 13,
6884.
Ostwald Ripening of an Alkane in H2O Emulsions Langmuir, Vol. 18, No. 26, 2002 10089

Table 2. Ostwald Ripening Rates as a Function of Added

Surfactant for Several Undecane, Dodecane, and Decane
Emulsions
ratio of
overall ripening rate
surfactant after addition
concentration concentration to the rate
of added after addition before addition
emulsion SDBS (M) (M) of surfactant
Undecane
UB1 0 2.0 × 10-2
UB2 1.00 × 10-2 1.7 × 10-2 0.97
UB3 2.50 × 10-2 2.3 × 10-2 0.88
UB4 5.00 × 10-2 3.0 × 10-2 0.99
Figure 4. Rate enhancement factors as a function of overall
UB5 7.50 × 10-2 3.8 × 10-2 1.06
surfactant concentration. Undecane emulsions prepared under
UB6 1.00 × 10-1 4.7 × 10-2 1.21
high-shear conditions.
UB7 1.25 × 10-1 5.5 × 10-2 1.07
UB8 1.50 × 10-1 6.3 × 10-2 1.18
predicted by eq 1 (i.e., 6.5 nm3/s for the undecane
emulsions13) are reported in Table 1 as rate enhancement Dodecane
Do1 0 2.0 × 10-2
factors. Note that the oil volume fraction of the studied Do2 1.00 × 10-2 1.7 × 10-2 0.88
emulsion (0.01) is small enough to exclude a volume Do3 2.50 × 10-2 2.3 × 10-2 0.89
fraction-dependent term in eq 1.23 Do4 5.00 × 10-2 3.0 × 10-2 1.08
In Figure 4, the rate enhancement factors are given as Do5 7.50 × 10-2 3.8 × 10-2 1.22
a function of the surfactant concentration, and they show Do6 1.00 × 10-1 4.7 × 10-2 1.22
no systematic dependence on the surfactant concentration. Do7 1.50 × 10-1 6.3 × 10-2 1.63
The numerical values of 1.15 to 1.46 are consistent with Decane
the model whereby the continuous phase consists of a D1 0 2.0 × 10-2
dispersion of small oil droplets with an average radius D2 2.50 × 10-2 2.3 × 10-2 0.93
typical of the size of a micelle.13 This model implies that D3 5.00 × 10-2 3.0 × 10-2 0.88
D4 7.50 × 10-2 3.8 × 10-2 0.72
there is no direct exchange of oil molecules between D5 1.00 × 10-1 4.7 × 10-2 0.78
micelles and droplets. The exchange of oil is achieved only D6 1.50 × 10-1 6.3 × 10-2 0.86
by the diffusion of individual oil molecules through the
continuous phase. Since these emulsions are prepared
under the high-shear conditions of the microfluidizer, one
can assume that the alkane and the surfactant are
distributed in a quasi-equilibrium state between the
micelles (swollen by alkane) and the larger emulsion
droplets. The equilibrium (alkane) solubility in a continu-
ous phase of small droplets is given by Kelvin’s equation:

Cm/C(∞) ) exp(R/a) (3)

In eq 3, a is the droplet radius. Assuming that the

enhancement of the ripening rates is due to the increase
in solubility predicted by Kelvin’s equation, the average
radius of the micelles (swollen by alkane) can be estimated
by eq 3, yielding values ranging from 4.5 to 12.3 nm. The
average enhancement factor amounts to 1.31, which
corresponds to a radius of 6.3 nm. Note that for a 0.1 M
SDBS solution saturated with undecane the measured
radius was 4.9 nm.
The fact that the ripening rates do not vary with the
micelle concentration together with the absolute values
of these rates confirms that the only aging process is due
to molecular transport of alkane through the continuous
phase and that there is no significant contribution from
a transport mechanism by the micelles. The emulsions
behave as if the surfactant and the alkane molecules are
distributed between micelles and the larger emulsion
droplets in a quasi-equilibrium state. The only factor
disturbing this quasi-equilibrium is the Ostwald ripening
process.
In the second step, the ripening of eight new undecane,
seven dodecane, and six decane emulsions was investi-
gated. Three mother emulsions (undecane, dodecane, and
decane) with 2 × 10-2 M SDBS were prepared in the second
way. Samples of 2 mL of these emulsions were monitored
until the average radius was about 50 nm. At that moment,
(23) Voorhees, P. J. Stat. Phys. 1985, 38, 231.
Figure 5. Evolution of a3 with time for the undecane emulsions
(UB1 bottom to UB8 top) prepared under high-shear conditions
and to which extra surfactant was added at different concen-
trations. For clarity, the different series have been translated
along the ordinate over 2 × 105 nm3.
1 mL of a surfactant solution of a different concentration
was added. In these experiments, the particle size of the
undiluted emulsions was determined. The details are
reported in Table 2.
The results of the monitoring of the droplet size as a
function of time are displayed in Figures 5 to 7 and Table
2. Ripening rates are determined before and after the
addition of the surfactant solution. The ratios of these
rates are reported in Table 2 and Figure 8. It is clear that
the ripening process is not affected by the addition of extra
surfactant, except for emulsion Do7 with the highest added
surfactant concentration. These rates fluctuate around 1
and show no systematic dependence on the added sur-
factant concentration. Again, this confirms that there is
no significant contribution from a transport mechanism
by the micelles.
An enhanced ripening by factors up to 20, after the
addition of surfactant, was on the contrary observed with
the nonionic surfactant Tween 2018 at all investigated
concentrations of added surfactant. A qualitative expla-
10090 Langmuir, Vol. 18, No. 26, 2002
Figure 6. Evolution of a3 with time for the dodecane emulsions
(Do1 bottom to Do7 top) prepared under high-shear conditions
and to which extra surfactant was added at different concen-
trations. For clarity, the different series have been translated
along the ordinate over 2 × 105 nm3.
Figure 7. Evolution of a3 with time for the decane emulsions
(D1 bottom to D6 top) prepared under high-shear conditions
and to which extra surfactant was added at different concen-
trations. For clarity, the different series have been translated
along the ordinate over 2 × 105 nm3.
Figure 8. Ratio of the ripening rate after surfactant addition
to the rate before addition as a function of overall surfactant
concentration for undecane ()), dodecane (0), and decane (4)
emulsions prepared under high-shear conditions.
nation for the enhancement is the following.18 Before
adding additional surfactant, there is in the already-
formed emulsion a quasi-equilibrium state whereby the
already-present surfactant and the alkane molecules are
distributed between micelles and the larger emulsion
droplets. The only factor disturbing this quasi-equilibrium
Nguyen Hoang et al.
is the Ostwald ripening process. On average, the alkane
is transported slowly from smaller droplets to larger ones
by molecular diffusion through the continuous phase. The
rate of this process is mainly determined by the alkane
solubility in the continuous phase (the factor C(∞) in eq
1). However, this quasi-equilibrium state is a dynamic
one whereby micelles and droplets are continuously broken
down and rebuilt. The addition of extra surfactant disturbs
this dynamic equilibrium. More alkane droplets and
micelles are broken down. During the evolution toward
a new quasi-equilibrium distribution of alkane and
surfactant, there are now on average more alkane
molecules present in the continuous phase. Hence, the
factor C(∞) in eq 1 is increased, resulting in an increase
in the OR rate.
It is striking that the addition of the anionic surfactant
SDBS to already-formed emulsions stabilized by SDBS
does not affect the Ostwald ripening. The addition of Tween
20 to emulsions stabilized by Tween 20, however, has a
large effect on the ripening behavior.18 It is not very likely
that this difference is due to the difference in solubility
of the alkanes in the surfactant solution. The solubilities
of undecane in SDBS and Tween 20 are relatively low; a
0.1 M solution of Tween 20 solubilized only about twice
as much undecane as a 0.1 M SDBS solution.
Another difference is that the SDBS micelles do not
contribute to the transport of alkane from smaller to larger
emulsion droplets, whereas there is a small but significant
contribution to the transport from Tween 20 micelles.
The difference in the nature of the interactions, long-
range electrostatic repulsions for the anionic SDBS
compared to mainly steric repulsion for the nonionic Tween
20, is probably more important. The result of the elec-
trostatic repulsion is that it better protects the emulsions
stabilized by SDBS against the external perturbation of
the addition of surfactant.
4. Conclusions
The rate of Ostwald ripening in alkane emulsions
stabilized by the anionic surfactant SDBS was determined.
When the emulsions are prepared under high-shear
conditions using a microfluidizer, the ripening rates are
independent of the micellar surfactant concentration in
the continuous phase. The aging process is due to
molecular transport of alkane through the continuous
phase, and there is no significant contribution from a
transport mechanism by the surfactant micelles. The
emulsions behave as systems consisting of large alkane
droplets in quasi-equilibrium with micelles saturated with
alkane. The only process disturbing the quasi-equilibrium
is the Ostwald ripening of the larger droplets. When
micellar surfactant solutions are added to an already-
formed emulsion, the Ostwald ripening process is not
affected, confirming the fact that the micelles do not
contribute to the transport of alkane molecules.
LA0204545