2162 Langmuir 1996, 12, 2162-2168

Absolubilization of Styrene and Isoprene in

Cetyltrimethylammonium Bromide Admicelle on
Precipitated Silica
Boonyarach Kitiyanan,† John H. O’Haver,*,‡ Jeffrey H. Harwell,‡ and
Somchai Osuwan†
The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand, and
School of Chemical Engineering and Materials Science, University of Oklahoma,
Norman, Oklahoma 73019

Received September 20, 1995. In Final Form: January 25, 1996X

The adsolubilization of styrene, isoprene, and mixtures of styrene and isoprene into cetyltrimethy-
lammonium bromide (CTAB) bilayers (admicelles) on precipitated silica is investigated. The results show
that the styrene adsolubilization constant is nearly unchanged with increasing styrene equilibrium
concentration in the aqueous phase, while the isoprene adsolubilization constant increases with increasing
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isoprene partial pressure. The adsolubilization constants suggest that styrene adsolubilizes into both the
palisade layer and the core of the admicelle, while isoprene adsolubilizes into the palisade layer. In the
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co-monomer system styrene adsolubilization is slightly increased in the presence of isoprene but isoprene
adsolubilization is significantly enhanced in the presence of styrene; however, the adsolubilization isotherms
of both monomers have increasing slopes in the co-monomer system and show that there is a synergistic
effect, possibly due to swelling of the admicelle due to the addition of adsolubilizate.

Introduction show improved rubber physical properties, including

Layers of adsorbed surfactants on a solid surface can
be considered as a two-dimensional solvent. This concept
opens up a variety of applications, including both separa-
tion and reaction processes on the surface of the solid. A
previously explored separation process, known as admi-
cellar chromatography, has been examined recently for
environmental applications.1,2 Previously studied reaction
processes include both admicellar catalysis3 and admi-
cellar polymerization.4,5 Utilizing the latter process,
hydrophobic molecules concentrate and react within a
surfactant layer on a hydrophilic surface to form a polymer-
modified or copolymer-modified solid oxide surface.4-6
One of the substrates on which polymer films are thus
formed is precipitated, amorphous silica.5,6 This type of
silica is extensively used as a filler and reinforcer in shoe
soles and in tractor and off-road tire treads.7 The presence
of silica in rubber compounds provides a number of
advantages, such as improvement in tear strength,
reduction in heat buildup, and increase in compound
adhesion in multcomponent products, e.g. tires.7 Recently,
so-called “all-silica” tires have been touted as “green tires”
because their decreased rolling resistance results in
substantial reductions in fuel consumption and air pol-
lution.
Styrene-butadiene and styrene-isoprene copolymers
are the first copolymers used to modify the silica surface.6
When compared to unmodified silica, both modified silicas
* Author to whom correspondence should be addressed.
† Chulalongkorn University.
‡ University of Oklahoma.
X Abstract published in Advance ACS Abstracts, April 1, 1996.
(1) Barton, J. W.; Fitzgerald, T. P.; Lee, C.; O’Rear, E. A.; Harwell,
J. H. Sep. Sci. Technol. 1988, 23, 637.
(2) Nayyar, S. P.; Sabatini, D. A.; Harwell, J. H. Environ. Sci. Technol.
1994, 28, 1874.
(3) Yu, C.; Wong, D. W.; Lobban, L. L. Langmuir 1992, 8, 2582.
(4) Wu, J.; Harwell, J. H.; O’Rear, E. A. Langmuir 1987, 3, 531.
(5) O’Haver, J. H.; Harwell, J. H.; O’Rear, E. A.; Snodgrass, L. J.;
Waddell, W. H. Langmuir 1994, 10, 2588.
(6) Waddell, W. H.; O’Haver, J. H.; Evans, L. R.; Harwell, J. H. J.
Appl. Polym. Sci., in press.
(7) Barbin, W. W.; Rodgers, M. B. In Science and Technology of Rubber,
2nd ed.; Mark, J. E., Erman, B., Eirich, F. R., Eds.; Academic Press:
San Diego, 1994.
decreased cure time, increased tear strength, improved
elongation to break, and improved cut growth resistance.6
These results show the potential for economically modify-
ing silica by admicellar polymerization for use in elas-
tomers. Previous studies show that styrene-butadiene-
modified silicas perform the best, followed closely by
styrene-isoprene-modified silicas. For these reasons, it
is both scientifically interesting and industrially important
to more fully understand and quantify the amount of each
monomer that is available for polymerization on the silica
surface.
The co-adsolubilization of styrene-butadiene is inves-
tigated by O’Haver.8 His results show that butadiene both
adsolubilizes into admicelles on the silica surface and
condenses in the pores of the silica. The total uptake of
butadiene is greatly increased in the presence of styrene,
probably due to increased pore condensation. Unlike
butadiene, isoprene is a liquid at room temperature and
pressure. If this process of silica modification by admi-
cellar polymerization were taken to the production stage,
it would be advantagenous to use liquid monomers, e.g.
styrene and isoprene, and eliminate the use of butadiene.
Background
Adsorption of Surfactant on the Solid Oxide
Surface. The adsorption isotherm of ionic surfactants
on oxide surfaces is typically an elongated ‘S’-shaped curve
when one plots the log of the adsorbed surfactant density
versus the log of the equilibrium concentration of sur-
factant.10,11 Normally, this ‘S’-shaped isotherm can be
separated into four regions, as shown in Figure 1. Region
I corresponds to both very low concentration and low
adsorption of surfactant. This region is commonly referred
to as the Henry’s law region because the adsorbed
surfactant is considered to be in infinite dilution in the
(8) O’Haver, J. H. Ph.D. Dissertation, University of Oklahoma, 1995.
(9) Iler, R. K. The Chemistry of Silica; John Wiley & Sons Inc.: New
York, 1979.
(10) Somasundarun, P.; Fuerstenau, D. W. J. Phys. Chem. 1966, 70,
90.
(11) Scamehorn, J. F.; Schechter, R. S.; Wade, W. H. J. Colloid
Interface Sci. 1982, 85, 463.

S0743-7463(95)00783-9 CCC: $12.00 © 1996 American Chemical Society

Adsolubilization of Styrene and Isoprene
Figure 1. Typical adsorption isotherm of surfactants on solid
oxide surfaces.
surface phase and, thus, the interaction between molecules
of surfactants is negligible. Adsorbed surfactants in this
region are viewed as being adsorbed alone and not forming
any aggregates. Region II is distinguished by a sharply
increased isotherm slope relative to the slope in region I.
This increase in slope indicates the beginning of lateral
interactions between surfactant molecules, which result
in the formation of surfactant aggregates on the most
energetic surface patches.11 These adsorbed surfactant
aggregates are called admicelles12 or hemimicelles,10
depending upon whether the aggregates are viewed as
bilayers or monolayers. The admicelle is considered as a
local bilayer structure with a lower layer of head groups
adsorbed on the substrate surface and an upper layer of
head groups in contact with solution. The hemimicelle is
a monolayer structure having the head group adsorbed
on the surface while the tail group is in contact with the
aqueous phase. The transition point from region I to
region II, representing the first formation of adsorbed
surfactant aggregates, is called the critical admicelle
concentration (cac)12 or the hemimicelle concentration
(hmc).10
The slope of the isotherm decreases in region III. This
is thought to be caused by either repulsion between the
like-charged head groups on the surface or the beginning
of admicelle formation on lower energy surface patches.
Region IV is the plateau region, having almost constant
surfactant adsorption with increasing surfactant concen-
tration. Typically, the equilibrium surfactant concentra-
tion at the transition point from region III to region IV is
approximately at the critical micelle concentration (cmc).
The adsorption of surfactants on solid substrates is
controlled by several parameters, including the electro-
chemical nature of the substrate, the pH of the solution,
and the type of surfactant molecule. The net charge on
a solid oxide surface can be manipulated to be either
positive or negative by adjusting the pH of the contacting
aqueous solution because both hydrogen and hydroxyl ions
are potential determining ions for metal oxides. The pH
at which the net charge on the surface is zero is called the
point of zero charge (PZC). When the pH of the contacting
aqueous solution is below the PZC of the solid oxide surface,
the surface will be protonated and positively charged. On
the other hand, the oxide surface will be negatively charged
at a pH above the PZC. For instance, silica, having 2 e
PZC8 e 3, will be negatively charged when the pH of the
aqueous solution exceeds 3. Therefore, cationic surfac-
tants such as cetyltrimethylammonium bromide (CTAB)
adsorb readily on the surface of silica when the pH of the
contacting aqueous phase is greater than 3.
Adsolubilization. The partitioning of organic solutes
from aqueous solution into the interior of adsorbed
(12) Harwell, J. H.; Hoskins, J. C.; Schechter, R. S.; Wade, W. H.
Langmuir 1985, 1, 251.
Langmuir, Vol. 12, No. 9, 1996 2163
Figure 2. Phenomena of solubilization and adsolubilization.
surfactant aggregates is termed adsolubilization. This
phenomenon is the surface analog of solubilization, with
adsorbed surfactant bilayers playing the role of micelles,
as shown in Figure 2. The suggested definition of
adsolubilization is “the incorporation of compounds into
surfactant surface aggregates, which compounds would
not be in excess at the interface without surfactant.”13
In 1982, Nunn et al.14 presented visual evidence of
pinacyanol chloride, a dye of the cyanide class, adsolu-
bilized into the organic environment of adsorbed surfac-
tants. When pinacyanol chloride was dissolved in aqueous
solutions in which the surfactant was below the cmc, the
solution was red in color, indicating that the dye was in
an aqueous environment. When the dye was dissolved in
organic solvents or in aqueous solutions of surfactants
above the cmc, a blue color occurred, indicating that the
dye was in an organic environment. The blue color also
appeared on an alumina surface on which anionic sur-
factants had been adsorbed and the surfactant concentra-
tion in the aqueous phase was below the cmc. When the
bulk surfactant concentration was above the cmc, the blue
color was observed both on the surface of the alumina and
in the aqueous phase. This indicated the partitioning of
pinacyanol between micelles and admicelles and showed
that the interior of the admicelle is similar in nature to
the interior of micelles.
To examine the structure of the adsorbed bilayer of
Triton X-100 (octylphenoxyethanol with an average of
9-10 oxyethylene units), Levitz et al.15,16 used fluorescence
decay spectroscopy and pyrene as a probe. This work
also supported the hydrophobic environment of the
admicelle’s core and confirmed the adsolubilization of
hydrophobic molecules. At low levels of adsorbed sur-
factant, the probe behaved similarly to patchwise-adsorbed
micelles on the surface. At higher surfactant concentra-
tions, the result showed that the adsorbed surfactant phase
seems to be continuous on the silica surface.
Subsequently, O’Haver et al. systematically studied the
adsolubilization of both a series of alcohols and a series
of alkanes into admicelles on alumina.17 For the adsolu-
bilization of alcohols, the ratios of alcohol to SDS molecules
in the admicelles were very high at low levels of surfactant
adsorption. As the surfactant adsorption was increased,
these ratios decreased to a value which is similar to the
(13) Scamehorn, J. F.; Harwell, J. H. In Surfactants in Chemical/
Process Engineering; Wasan, D. T., Ginn, M. E., Shah, D. O., Eds.;
Marcel Dekker, Inc.: New York, 1988.
(14) Nunn, C. C.; Schechter, R. S.; Wade, W. H. J. Phys. Chem. 1982,
86, 3271.
(15) Levitz, P.; Van Damme, H.; Keravis, D. J. Phys. Chem. 1984,
88, 2228.
(16) Levitz, P.; Van Damme, H. J. Phys. Chem. 1986, 90, 1302.
(17) O’Haver, J. H.; Yeskie, M. A.; Harwell, J. H. ACS Symp. Ser.,
in press.
2164 Langmuir, Vol. 12, No. 9, 1996
ratios of alcohol to surfactant molecules in SDS micelles.
Below the cmc (in regions I, II, and III) the amount of
surfactant adsorption was not only considerably increased
in the presence of alcohol but also increased with increas-
ing alcohol molecular weight. Although surfactant ad-
sorptions were increased below the plateau region,
adsorptions in the plateau region (region IV) were slightly
decreased.
O’Haver et al. also observed that alkanes adsolubilized
to a high degree in SDS admicelles. Moreover, alkane
adsolubilization increased with increased surfactant
adsorption. It was observed, as predicted, that the
standard-state free energy of alkanes adsolubilized into
the SDS admicelles is approximately the same as for the
alkanes solubilized into micelles. This further indicated
that admicelles have an interior similar to the micellar
interior.
To explain the results of alcohol adsolubilization, a
“patchy bilayer” of adsorbed surfactant was proposed by
Lee et al.18 They further proposed that the adsorbed
surfactant in regions II and III of the isotherm is present
at disk-shaped aggregates. Because of an alcohol’s polar
end group, the disklike admicelles model explained how
alcohols could be adsolubilized into two sites of these
admicelles. One site is between the head groups of the
surfactant; this site is also present in micelles. The other
site, which is not present in micelles, is the hydrophobic
perimeter arising from the formation of the patchy,
disklike admicelles. The fraction of alcohols adsolubilized
at the perimeter can only be significant when the patchy
aggregates are small, so the ratios of adsolubilized alcohols
to adsorbed surfactant are very high at low surfactant
adsorption. Furthermore, the adsolubilized alcohols at
the perimeter increased the hydrophobicity of the surface
phase, so the surfactant adsorption is higher in the
presence of alcohols. As the chain length of the alcohol
increased, this hydrophobic contribution became greater
and, therefore, resulted in enhanced surfactant adsorption.
Admicelles have also been used as two-dimensional
templates for reactions. Yu et al.3 studied sodium dodecyl
sulfate (SDS) adsorbed on high surface area alumina used
to catalyze the hydrolysis of trimethyl orthobenzoate in
a process called admicellar catalysis, the surface analog
to micellar catalysis. Their results show that the highest
specific activity of the admicelles is less than the maximum
specific activity of the corresponding micelles but that the
admicelle activity increases with increasing surface
coverage above a certain value.
Another successful application of admicelles is admi-
cellar polymerization. Polymerization of adsolubilized
styrene monomer in SDS admicelles on the surface of
alumina was investigated by Wu et al.4 The process for
creating these ultrathin polymer films was considered to
consist of four steps. Step one is the forming of admicelles,
providing both the high surface coverage and a template
for dissolving the reactants. Step two in this process
involves the adsolubilization of monomer into the admi-
celle. Because organic monomers have limited solubility
in water, they preferentially partition into the hydrophobic
interior of admicelles. Step three is the in-situ polym-
erization of the adsolubilized monomer. The final step is
the removal of excess surfactant in order to expose the
polymer films.
Gaseous and polar (more water soluble) monomers can
also be successfully used in this process. The investigation
of tetrafluoroethylene (TFE) adsolubilized and polymer-
ized in perfluorinated surfactant admicelles on alumina
was carried out by Lai.19 Subsequently, more polar
(18) Lee, C.; Yeskie, M. A.; Harwell, J. H.; O’Rear, E. A. Langmuir
1990, 6, 1758.
Kitiyanan et al.
monomers and co-monomers were used to form polymer
films on precipitated silica with CTAB as the surfactant.5,8
Experimental Section
Materials. All Chemicals were obtained commercially and
used as received. Cetyltrimethylammonium bromide (CTAB),
at a purity of 99%, styrene (99%), and isoprene (99%) were
obtained from Aldrich Chemical Company, Inc. (Milwaukee, WI).
Hi-Sil 255, a porous, amorphous, precipitated silica was received
from PPG-Siam Silica Co., Ltd. (Rayong, Thailand) with a
reported surface area of 170 m2/g, a mean particle size of 18.95
µm, and 100% surface-silanol group coverage.
Methods. The quantity of adsorbed CTAB on Hi-Sil 255 was
calculated by the concentration difference method. Using a mass
balance and the concentration of CTAB in the aqueous feed
solution and the equilibrium supernatant, the amount of adsorbed
surfactant can be calculated. The initial aqueous solution was
adjusted to pH 8 using sodium hydroxide solution. Although a
more basic solution, (e.g. higher than pH 8) causes a higher driving
force for CTAB adsorption on silica, the solubility of silica in
alkaline solution reaches a minimum close to pH 8 and increases
rapidly above the value.9 The CTAB concentration was deter-
mined via titration against standard sodium dodecyl sulfate (SDS)
solution in a two-phase titration.20
In order to determine the adsolubilization of styrene, feed
solutions with known CTAB and styrene concentrations in pH
8 water were brought into contact with samples of amorphous
precipitated silica of known mass in sealed glass vials (42 mL
empty volume borosilicate glass vials with screw caps and PTFE-
faced silicone septa obtained from Baxter Diagnostics, Inc.,
McGaw Park, IL). The system was allowed to equilibrate at 30
°C for at least 48 h. After equilibration, the supernatant was
decanted and centrifuged. The styrene concentration was then
measured by UV/vis spectrophotometry at 280 nm. A Bausch
& Lomb Spectronic 1001 spectrophotometer was used to deter-
mine UV absorbance of styrene at 280 nm. The amount of
adsolubilized styrene was calculated from the concentration
difference of styrene in the solution from the feed and after
equilibration.
The solute vapor pressure apparatus used to find isoprene
solubility in water and isoprene adsolubilization was similar to
one developed by Christian and co-workers.21,23 In this experi-
ment, this apparatus consisted of a glass vessel having a working
space of 850 mL, a screw-on nylon cap, a pressure transducer,
an HPLC injector, a vacuum pump, a water temperature
controller, and a computer interface recording the pressure of
the system and controlling injection of isoprene into the system.
Figure 3 shows schematically the significant parts of the
apparatus. The vessel and cap were custom-ordered from Ace
Glass Inc. (Vineland, NJ). The HPX811-020AV pressure trans-
ducer and WB-AASC-GP high-speed interface card were obtained
from Omega Engineering, Inc. (Stamford, CT). The ISIS Auto
inject actuator and Model 7010 Rheodyne valve were obtained
from Altech (Deerfield, IL). The Dyna-Sense Model 2149
temperature controller was obtained from Cole Parmer, and the
heating unit was obtained from Fisher Scientific. The PTFE
diaphragm pump and pump motor used to circulate the bulk
liquid through the UV cell were obtained from Cole Parmer (Niles,
IL). The UV flow cell, model 71-Q-10-T, was purchased from
Starna Cells, Inc. (Atascadero, CA). An HPLC solvent filter from
Rainin (Emeryville, CA) was used to exclude silica from getting
into the pump/UV cell circuit.
The partial pressure of isoprene was calculated from the
difference between the total pressure and the vapor pressure of
pure water at the experimental conditions. The solubility of
isoprene in water at 30 °C was determined by recording the
pressure of the sealed reaction vessel containing 500 mL of
degassed water. The system was first allowed to reach a steady
temperature of 30 °C and was then evacuated to the vapor
(19) Lai, C.-L.; Harwell, J. H.; O’Rear, E. A.; Komatsuzaki, S.; Arai,
J.; Nakakawaji, T.; Ito, Y. Langmuir, in press.
(20) Barr, T.; Oliver, J.; Stubbings, W. V. J. Soc. Chem. Ind., London
1948, 67, 45.
(21) Tucker, E. E.; Christian, S. D. J. Chem. Thermodyn. 1979, 11,
1137.
(22) Smith, L. S.; Tucker, E. E.; Christian, S. D. J. Phys. Chem. 1981,
85, 1120.
(23) Tucker, E. E.; Christian, S. D. J. Phys. Chem. 1977, 81, 1295.
Adsolubilization of Styrene and Isoprene
Figure 3. Schematic of the solute vapor pressure apparatus.
pressure of water (0.615 psia). Then, 200 µL of isoprene was
injected into the system and left allowed to equilibrate; the
injections were continued until the system’s pressure reached
the vapor pressure of isoprene. In order to see the interaction
between isoprene and unmodified silica, the procedure was
repeated, except that this time 40 g of Hi-Sil 255 was added into
the sealed vessel containing 500 mL of distilled water.
For the adsolubilization of isoprene, a feed solution consisting
of 500 mL of pH 8 water, 7.2 g of CTAB, and 40 g of silica was
loaded into the vessel, stirred, and allowed to equilibrate for at
least 12 h. The CTAB concentration was selected so that no
micelles would be present in the bulk phase. The system was
then evacuated repeatedly to the vapor pressure of the system
until no increase in pressure was noted when the system was
allowed to sit. Water losses due to evacuation were estimated
on the basis of the volume of the vapor phase and assuming
saturated vapor. These losses represent less than 0.01% and
were therefore ignored. Isoprene was then injected into the
system via the HPLC injector in 200 µL increments, until the
system equilibrated at the vapor pressure of the isoprene. The
system was allowed to reach equilibrium between injections.
The co-adsolubilization of isoprene and styrene was determined
by dissolving styrene and 7.2 g of CTAB in 500 mL of pH 8 water
and contacting it with 40 g of silica in the vessel. The system
was allowed to equilibrate for 12 h at 30 °C before it was
evacuated. Styrene losses, based upon losses in the vapor phases,
were estimated and found to be negligible, because the styrene
vapor pressure is very low. Isoprene was then injected into the
system as previously described. The isoprene adsolubilization
was calculated from a mass balance and the total pressure
recorded from the transducer. The styrene concentration in the
supernatant was determined by measuring the UV absorbance
at 280 nm for the liquid phase circulated through the flow cell.
Styrene adsolubilization was then determined from a mass
balance. The UV adsorbance readings were done manually after
each isoprene injection had equilibrated.
Results and Discussion
CTAB Adsorption on Hi-Sil 255. The CTAB adsorp-
tion isotherm on Hi-Sil 255 is shown in Figure 4. The
isotherm illustrates the characteristics of regions II, III,
and IV. The slope of the isotherm is greater than 1 from
a concentration of CTAB in the aqueous solution of 70 µM
to a concentration of 120 µM. This very high slope
indicates the onset of CTAB aggregation on the surface
of the silica, which occurs either at or below 70 µM. From
the plateau region data, the maximum adsorption of CTAB
on Hi-Sil 255 is approximately 550 µmol/g. The reported
specific surface area of Hi-Sil 255 from the manufacturer
is 170 m2/g. On the basis of monolayer coverage, this
silica gives a coverage of 1.95 molecule/nm2 or 51 Å2/
molecule. These values can be compared to those for
Langmuir, Vol. 12, No. 9, 1996 2165
Figure 4. CTAB adsorption isotherm on Hi-Sil 255.
Figure 5. Comparison of CTAB adsorption on Hi-Sil 255 and
Hi-Sil 233.
tetradecyltrimethylammonium bromide and octadecyl-
trimethylammonium bromide, which respectively have
61 and 64 Å2/molecule for the area per molecule at surface
saturation of surfactants at the water-air interface.24 We
estimate the area/head group of CTAB to be 62 Å2. If the
admicelles were present over all of the surface, the area
per CTAB molecule should be =30 Å2. However, the CTAB
molecule is too large to adsorb in the very narrow pores
of this silica, so the observed area per head group on the
silica surface is greater than the area per head group
estimated for complete bilayer coverage. We believe,
therefore, that the aggregation of CTAB on the silica
surface is most likely in the form of a local bilayer
(admicelles) but that all the BET surface area is not
accessible to the CTAB.
Figure 5 presents a comparison of CTAB adsorption
(molecules per nm2) on Hi-Sil 255 and Hi-Sil 233 (another
precipitated silica), having specific surface areas of 170
and 145 m2/g, respectively.5 It should be noted that the
increase in the maximum CTAB adsorption is not linear
with respect to specific surface area. The adsorption
density of CTAB is 51 Å2/molecule on Hi-Sil 255 and 89
Å2/molecule on Hi-Sil 233.
Styrene Adsolubilization. The adsorption of styrene
on silica in water is also investigated. The result shows
that there is no significant adsorption of styrene on the
wet silica. The relation between the amount of adsolu-
bilized styrene and the equilibrium styrene concentration,
as well as the adsolubilization of styrene versus reduced
concentration, is shown in Figure 6. The reduced con-
centration is dimensionless, calculated by dividing the
equilibrium styrene concentration by the solubility of
styrene in water. As expected, when the equilibrium
concentration of styrene increases, the amount of adsolu-
bilized styrene increases.
(24) Rosen, M. J. Surfactants and Interfacial Phenomena, 2nd ed.;
Wiley Interscience: New York, 1989.
2166 Langmuir, Vol. 12, No. 9, 1996
Figure 6. Styrene adsolubilization versus styrene equilibrium
concentration and reduced styrene concentration.
Figure 7. Normalized adsolubilization equilibrium constant
versus styrene mole fraction.
The micellar solubilization equilibrium constant has
been defined as the ratio of the solute mole fraction in the
micelle to the equilibrium concentration of solute in bulk
aqueous solution.25,26 Analogously, this work defines the
adsolubilization equilibrium constant as Ki ) Xi/Cib, where
Ki is the adsolubilization equilibrium constant of the
adsolubilizate (i), Xi is the mole fraction of adsolubilizate
(i) in the admicelle, and Ci,b is the concentration of solute
(i) in the bulk aqueous phase (M).
In a work which studied the solubilization of decahy-
dronaphthalene (naphthane), naphthalene, and 1-naph-
thol in micelles,27 it was concluded that, with increasing
solute mole fraction in the bulk aqueous phase, the
partition coefficient, which is virtually the same as the
solubilization equilibrium constant, decreased for solutes
which primarily solubilize in the palisade layer and
increased for solutes which primarily solubilize in the
micelle core. For solutes believed to partition into both
the core and the palisade layer, the partition coefficient
remained relatively constant.
Figure 7 shows the relation between the normalized
adsolubilization equilibrium constant and the styrene mole
fraction in the admicelle, assuming a constant surfactant
adsorption of 500 µmol/g. Lee et al. have shown that the
presence of an adsolubilizate does not significantly affect
(25) Smith, G. A.; Christian, S. D.; Tucker, E. E.; Scamehorn, J. F.
J. Colloid Interface Sci. 1989, 130, 254.
(26) Mahmoud, F. A.; Higazy, W. S.; Christian, S. D.; Tucker, E. E.;
Taha, A. A. J. Colloid Interface Sci. 1989, 131, 96.
(27) Rouse, J.; Sabatini, D.; Deeds, N.; Brown, E.; Harwell, J. H.
Environ. Sci. Technol. 1995, 29, 2484.
Kitiyanan et al.
Figure 8. Solubility of isoprene in water.
the plateau adsorption of surfactant.18 The normalized
adsolubilization equilibrium constant is the adsolubili-
zation equilibrium constant divided by the value obtained
by extrapolation to a zero mole fraction, analogous to the
infinite dilution partition coefficient. The styrene ad-
solubilization equilibrium constant does not change
significantly. This implies that styrene is adsolubilized
into both the palisade layer and the core of the admicelle,
as would be expected from the known behavior of aromatics
in micelles.27 The maximum observed adsolubilization of
styrene is approximately 850 µmol/g, which corresponds
to a ratio of adsolubilized styrene to adsorbed surfactant
of about 1.7:1.
Isoprene Adsolubilization. The virial equation
truncated after the second virial coefficient is used to
determine the isoprene density as a function of partial
pressure.28 Therefore, the amount of isoprene in the
gaseous phase can be determined from the recorded
pressure. The solubility of isoprene in water is found by
following the pressure drop of each injection in the system
containing water, as shown in Figure 8. The solubility
data can be fit by the equation M ) 0.0000304(P2) +
0.000425(P) where M and P, respectively, are the molar
concentration of isoprene in the water and the partial
pressure of isoprene in the vapor (solid line in Figure 8).
The adsorption of isoprene on silica in water is also
investigated. The result shows that there is no significant
adsorption of isoprene on the wet silica. In the system
also containing surfactant, the adsolubilization of isoprene
is calculated utilizing a mass balance after the system is
equilibrated. Figure 9 shows the relationships between
the amount of adsolubilized isoprene and the equilibrium
partial pressure and the reduced pressure (the partial
pressure divided by the vapor pressure of pure isoprene
at 30 °C).
It should be noted that the time required to reach
equilibrium in the system containing silica and water or
water only is about 90 min, compared to about 2 h in the
system that also contains surfactant. The longer time
required to reach equilibrium in the presence of surfactant
may imply increased mass transfer resistance for the
isoprene that is transferring from the aqueous phase into
the admicelles in the silica’s pore. It may be due, however,
to transfer through the aqueous phase occurring at the
same rate but a larger amount being transferred when
surfactant is present. This longer equilibrium time in
the presence of surfactant is consistent qualitatively with
observations made for butadiene adsolubilization, but the
actual equilibrium time in the isoprene system is shorter
than that in the butadiene system.8 Similarly, gas phase
solutes take longer times to reach equilibrium than liquid
solutes for solubilization into micelles.
(28) Daubert, T. E.; Danner, R. P. Physical and Thermodynamic
Properties of Pure Chemicals: Data Compilation; Hemisphere Publishing
Corp.: New York, 1989.
Adsolubilization of Styrene and Isoprene
Figure 9. Isoprene adsolubilization versus isoprene partial
pressure and reduced pressure.
Figure 10. Normalized adsolubilization equilibrium constant
versus isoprene mole fraction.
Figure 11. Styrene adsolubilization in the presence of isoprene.
Using the estimated value of 500 µmol/g CTAB adsorp-
tion, the adsolubilization equilibrium constant is isoprene
is calculated and normalized. The normalized adsolubi-
lization equilibrium constant of isoprene is plotted against
the isoprene mole fraction in the admicelle, as shown in
Figure 10. The decreasing value with increasing mole
fraction implies that isoprene is preferentially adsolubi-
lized into the palisade layer of the admicelle.27 The
maximum observed adsolubilization of isoprene is ap-
proximately 550 µmol/g, which corresponds to a ratio of
adsolubilized isoprene to adsorbed surfactant of about 1:1.
Styrene-Isoprene Co-Adsolubilization. Figure 11
is the plot of styrene adsolubilization versus the equilib-
rium concentration of styrene in the aqueous phase at
various isoprene partial pressures. The adsolubilization
of styrene was slightly increased as isoprene was incre-
mentally injected into the system. However, the equi-
Langmuir, Vol. 12, No. 9, 1996 2167
Figure 12. Isoprene adsolubilization in the presence of styrene.
Figure 13. Styrene adsolubilization equilibrium constant in
the co-monomer system.
librium concentration of styrene decreases approximately
by half as the equilibrium partial pressure of isoprene
nears its vapor pressure. Because most of the added
styrene (about 95%) was already adsolubilized, with only
about 5% of the initial added styrene remaining in the
bulk aqueous phase, the amount of styrene adsolubili-
zation is relatively unchanged. The styrene adsolubili-
zation is actually higher in the presence of isoprene, for
a given bulk styrene concentration, than it would be in
the absence of isoprene.
The adsolubilization of isoprene for three different feed
concentrations of styrene is presented in Figure 12. It is
evident that the presence of styrene significantly enhances
the adsolubilization of isoprene: at the same isoprene
partial pressure, the amount of adsolubilized isoprene
increases with increasing styrene loading. Moreover, the
difference in isoprene adsolubilization between those
systems containing styrene and systems with isoprene
alone increases with increasing isoprene partial pressure.
The adsolubilization equilibrium constants of styrene
and isoprene at various styrene feed concentrations are
plotted versus the styrene and isoprene mole fractions in
Figures 13 and 14, respectively. The adsolubilization
equilibrium constant of styrene (KS) is approximately
constant at styrene feed concentrations of 0.005 18 and
0.0205 M, while KS increases with increasing styrene mole
fraction at a 0.0409 M styrene feed. For isoprene, the
adsolubilization equilibrium constant of isoprene (KI)
decreases with increasing mole fraction of isoprene at
styrene loadings of 0.005 18 and 0.0241 M, while KI is
almost constant at a styrene feed concentration of 0.0409
M. The above results suggest that, at low styrene loading,
styrene is adsolubilized into both the palisade layer and
the core of the admicelle, while isoprene is adsolubilized
primarily into the palisade layer. The results at high
styrene loading imply that styrene is adsolubilizing
primarily into the core of the admicelle, while isoprene is
2168 Langmuir, Vol. 12, No. 9, 1996 Kitiyanan et al.

Figure 14. Isoprene adsolubilization equilibrium constant in

the co-monomer system.

Table 1. Ratios of Adsolubilized Styrene and

Adsolubilized Isoprene to Adsorbed Surfactant, the
Ratio of Adsolubilized Styrene to Adsolubilized Isoprene,
and the Trends of both KS and KI
amount ratio of ratio of ratio of
of adsolubilized adsolubilized adsolubilized
loaded styrene to isoprene to styrene to
styrene adsorbed adsorbed adsolubilized Figure 15. Structure model of adsolubilized monomers at
(mole) CTAB CTAB isoprene KS KI styrene feed concentrations of (a) 0.005 18 M, (b) 0.0205 M, and
(c) 0.0409 M.
0.0044 0.21 1.11 0.187 constant decrease
0.0174 0.85 2.03 0.42 constant decrease One possibility is that, while styrene would compete
0.0348 1.7 3.69 0.46 increase constant with isoprene to stay in the palisade layer, styrene in the
core would increase the solubility of isoprene in the core.
Table 2. Some Physical Properties of Styrene and Because of their very low solubilities in water, both
Isoprene adsolubilizates should have hydrophobic interactions with
solubility dipole each other, resulting in higher adsolubilizations. Another
monomer MW molecular formula in water momenta (C‚m) possibility is that though pore condensation appears to be
styrene 104.15 C6H5CHCH2 3.07 mM at 4.3363 × 10-31 nearly absent in the isoprene alone system, it might be
25 °C present in the mixed-monomer system. Additional work
isoprene 68.11 CH2CCH3CHCH2 8.0 mM at 8.3391 × 10-31 needs to be done to answer this question more satisfac-
20 °C torily.
a From ref 28.
Conclusions
adsolubilizing into both the palisade layer and the core
CTAB adsorption at a feed pH of 8 on Hi-Sil 255, an
of the admicelle.
amorphous, precipitated silica, is found to have a plateau
From Figures 11 and 12, the adsolubilization isotherms
value of 550 µmol/g of silica or 1.95 molecules/nm2. Though
of both monomers have an increasing slope in the
the CTAB adsorption is believed to exist in the form of
co-monomer system. This significant increase in slope
fully formed admicellar aggregates, some of the surface
indicates that the monomer adsolubilization dramatically
area is in inaccessible pores resulting in lower CTAB
increases in the co-monomer system. One might reason-
adsorption. The adsolubilization equilibrium constant of
ably expect that, with two adsolubilizates in the palisade
styrene in the CTAB bilayer is almost constant with
layer, they would compete for adsorption sites, resulting
increasing styrene concentration, which suggests that
in decreased adsolubilization equilibrium constants for
styrene is adsolubilized into both the palisade layer and
both. This is clearly not the case. Because the silica is
the core of the admicelle. The ratio of adsolubilized styrene
composed of overlapping spheres, the silica surface is
to adsorbed CTAB at near saturation conditions is found
everywhere convex, like the outer layer of a lipid bilayer.
to be approximately 1.7 at bulk concentrations near the
One possible explanation of the synergism is that as the
solubility of styrene in water.
bilayer becomes swollen by solubilized monomer, the area
The adsolubilization equilibrium constant of isoprene
per surfactant head group in the admicelle increases,
decreases with increasing isoprene mole fraction in the
thereby increasing the volume of the palisade layer.
admicelle; in analogy to the behavior of alkanes in micelles,
A CTAB admicelle, with extended 16 carbon atom
the isoprene is therefore believed to be adsolubilized into
chains, has sufficient room for two monomers of styrene
the palisade layer of the admicelle. The ratio of adsolu-
or isoprene to be adsolubilized by one surfactant molecule.
bilized isoprene to adsorbed CTAB at near saturation
From the trends shown by the styrene and isoprene
conditions is about 1:1.
equilibrium adsolubilization constants, KS and KI (Table
In the co-monomer system, while the total amount of
1), as isoprene adsolubilization increases, the styrene may
styrene adsolubilization does not increase significantly
begin to preferentially partition into the core. Further-
with increased isoprene adsolubilization, the styrene
more, by comparing the solubility in water and the dipole
equilibrium concentration decreases significantly. In
moment of both monomers (Table 2), isoprene can be seen
contrast, in the presence of styrene, isoprene adsolubi-
to have a higher polarity than styrene; this suggests that
lization significantly increases; possible mechanisms for
adsolubilized isoprene would stay closer to the CTAB head
this are proposed.
group than adsolubilized styrene. A suggested model is
shown in Figure 15. LA950783F