J Surfact Deterg (2007) 10:269–277
DOI 10.1007/s11743-007-1045-3
ORIGINAL ARTICLE
Adsorption of Anionic–Cationic Surfactant Mixtures on Metal
oxide Surfaces
A. Upadhyaya Æ E. J. Acosta Æ J. F. Scamehorn Æ
D. A. Sabatini
Received: 6 June 2007 / Accepted: 29 August 2007 / Published online: 12 October 2007

AOCS 2007
Abstract This research evaluates the adsorption of
anionic and cationic surfactant mixtures on charged metal
oxide surfaces (i.e., alumina and silica). For an anionic-rich
surfactant mixture below the CMC, the adsorption of
anionic surfactant was found to substantially increase with
the addition of low mole fractions of cationic surfactant.
Two anionic surfactants (sodium dodecyl sulfate and
sodium dihexyl sulfosuccinate) and two cationic surfac-
tants (dodecyl pyridinium chloride and benzethonium
chloride) were studied to evaluate the effect of surfactant
tail branching. While cationic surfactants were observed to
co-adsorb with anionic surfactants onto positively charged
surfaces, the plateau level of anionic surfactant adsorption
(i.e., at or above the CMC) did not change significantly for
anionic–cationic surfactant mixtures. At the same time, the
A. Upadhyaya
Nanofilm Ltd, 10111 Sweet Valley Dr, Valley View,
OH 44125, USA
E. J. Acosta
Department of Chemical Engineering and Applied Chemistry,
University of Toronto, 200 College Street, Toronto,
ON, Canada M5S 3E5
J. F. Scamehorn
School of Chemical, Biological and Materials Engineering.
T-335 Sarkeys Energy Center, 100 E. Boyd St.,
University of Oklahoma, Norman, OK 73019, USA
J. F. Scamehorn
D. A. Sabatini
Institute for Applied Surfactant Research,
University of Oklahoma, Norman, OK 73019, USA
D. A. Sabatini (&)
School of Civil Engineering and Environmental Science,
Rm. 334, Carson Engineering Center, 202 West Boyd,
The University of Oklahoma, Norman, OK 73019-0631, USA
e-mail: sabatini@ou.edu
adsorption of anionic surfactants onto alumina was dra-
matically reduced when present in cationic-rich micelles
and the adsorption of cationic surfactants on silica was
substantially reduced in the presence of anionic-rich
micelles. This demonstrates that mixed micelle formation
can effectively reduce the activity of the highly adsorbing
surfactant and thus inhibit the adsorption of the surfactant,
especially when the highly adsorbing surfactant is present
at a low mole fraction in the mixed surfactant system. Thus
surfactant adsorption can be either enhanced or inhibited
using mixed anionic–cationic surfactant systems by vary-
ing the concentration and composition.
Introduction
Mixtures of anionic and cationic surfactants are known to
exhibit extraordinary synergism, as evidenced by the
ultralow critical micelle concentrations (CMCs) and
interfacial tension values produced by these systems [1].
Use of anionic and cationic surfactant mixtures has been
evaluated in the following areas: simultaneous washing and
softening, analytical chemistry, enhanced oil recovery and
pharmaceutical applications [2–4], wastewater treatment
[5], textile wetting and detergency [6]. Further, the
adsorption of surfactants at the solid/liquid interface is
fundamentally important in many applications, including
detergency, froth flotation, paper manufacturing and phar-
maceutical production [7–10].
Numerous researchers have evaluated cationic surfac-
tant adsorption on silica and other negatively charged
surfaces [11–20]. Similarly, a number of studies have
evaluated the adsorption of anionic surfactants on posi-
tively charged surfaces [21–29]. While the adsorption of
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individual surfactants has been studied extensively, far less
research has evaluated surfactant adsorption from mixed
anionic–cationic surfactant systems; this is due largely to
the tendency of anionic or cationic surfactants to precipi-
tate [30–32]. Nonetheless, Huang et al. [33], Schwuger
et al. [34], Muller and Krempl [35] and Paria et al. [36]
have demonstrated that adsorption of anionic and cationic
surfactants is affected by the presence of oppositely
charged surfactants. Since cationic surfactants are bacteri-
cides [37] and fabric softeners [38], detergent formulations
that incorporate these properties are of great interest. By
contrast, in enhanced oil recovery or in subsurface reme-
diation, surfactant adsorption onto solid surfaces can result
in a substantial loss of surfactant from solution [39] and
decreased system performance. Thus, any method that
minimizes surfactant adsorption will be welcome so as to
reduce surfactant losses and cost. Since anionic–cationic
surfactant mixtures greatly reduce the monomer concen-
tration necessary to form mixed micelles [32], adsorption
in these systems is of great interest.
The first hypothesis of this work is that surfactant
adsorption is increased by using mixed anionic–cationic
surfactant systems. The first objective of this work is to
evaluate how surfactant adsorption is impacted when a
cationic surfactant is added to pre-adsorbed anionic sur-
factant on alumina. The second objective of this work is to
demonstrate that, when present in mixtures, surfactants can
adsorb onto like-charged surfaces (i.e., cationic surfactants
can adsorb on positively charged surfaces and anionic
surfactants on negatively charged surfaces when present in
mixed surfactant systems). These results will be especially
interesting for applications where the goal is to increase the
overall surfactant adsorption to achieve a desired result
(e.g., increased adsolubilization). The second hypothesis is
that when anionic surfactants are present at low mole
fractions in cationic-rich mixtures above the CMC, the
anionic surfactant will be located primarily in cationic-rich
micelles and their adsorption onto positively charged sur-
faces will be minimized. Similarly, it was hypothesized
that cationic surfactant adsorption can be substantially
reduced on negatively charged surfaces when present in
anionic-rich surfactant mixtures above the CMC. Thus, the
third objective of this research is to demonstrate that it is
possible to minimize the adsorption of anionic surfactants
on a positively charged surface and cationic surfactants on
a negatively charged surface by using surfactant mixtures.
These results will be especially interesting for applications
where adsorption is undesirable (e.g., cationic surfactant
adsorption onto cotton fabrics during detergency) but
where the anionic–cationic surfactant mixture system has
desirable characteristics (e.g., lower CMC). By ‘‘hiding’’
the cationic surfactant in the anionic-rich micelle it was
possible to minimize the aqueous activity of the cationic
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J Surfact Deterg (2007) 10:269–277
surfactant and thus minimize the cationic surfactant
adsorption on the negatively charged surface.
The cationic surfactant dodecylpyridinium chloride
(DPCl) was selected for study in this research because of
its common use in previous studies of mixed anionic–cat-
ionic surfactant systems [2]. The second cationic surfactant
studied in this research, benzethonium chloride (BCl), was
selected because of its branched and unbalanced tails (tails
with different number of alkyl groups); it is also a common
biocide and disinfectant [37] and has been used in deter-
gents [40] and deodorants [41]. The anionic surfactants
used in this work were sodium dihexyl sulfosuccinate
(SDHS) and sodium dodecyl sulfate (SDS). The SDS is an
anionic surfactant commonly used in industry and in a
relevant previous research project [2]. The SDHS was
selected because it is a branched surfactant and a common
choice for oil solubilization in environmental remediation
studies [42–44].
In the present work, low concentrations of dodecylpy-
ridinium chloride (DPCl) and benzethonium chloride (BCl)
were added onto alumina pre-adsorbed with sodium
dodecylsulfate (SDS) and sodium dihexylsulfosuccinate
(SDHS). Similarly, low concentrations of SDS were added
to silica pre-adsorbed with DPCl. Pre-adsorbed systems
were evaluated in an effort to avoid precipitation problems,
which occur if the anionic and cationic surfactant were
added into solution at the same time. In addition, the
adsorption of anionic surfactants (SDHS and SDS) on
virgin (i.e., no pre-adsorption) alumina was studied when
present in cationic-rich surfactant mixtures. Similarly,
adsorption of cationic surfactant (DPCl) in SDHS rich
mixtures was carried out on virgin silica.
Experimental Section
Materials
The DPCl (98% active) and SDS (98% active) were
obtained from Aldrich Chemical Company (Milwaukee,
WI). The SDHS was obtained from FLUKA Chemical
Company Ltd (Buchs, Switzerland) as an 80% solution of
dihexyl sulfosuccinate sodium salt by weight in water. The
BCl (97% active), trade name Hyamine, was obtained from
Aldrich Chemical Company (Milwaukee, WI). All the
surfactants were of research grade and were used as
received. The structure and properties of these surfactants
are illustrated in Table 1.
The alumina used in this study was supplied by Aldrich
Chemical Company (Milwaukee, WI) as an activated neutral
gamma aluminum oxide (Brockmann I grade). The powder
consisted of porous, quasi-spherical particles with manu-
facturer specified pore diameter of around 58 Å, a specific
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Table 1 Structure and properties of surfactants

Surfactant Surfactant Molecular Molecular Molecular structure Linear/branched
abbreviation formula weight (g/mol)

Sodium Dodecyl SDS C12H25SO4Na 288 SO4Na Linear

Sulfate

O
Sodium Dihexyl SDHS C16H30O4SO3Na 376 Branched
Sulfosuccinate

O
O
SO3Na

O
Dodecyl Pyridinium DPCl C17H31NCl 298 Cl- Linear
Chloride N+

Benzethonium BCl C27H42NO2Cl 448 Cl- Branched

Chloride O
O N
+

surface area of around 155 m2/g and particle size of *150
mesh. The surface area of the alumina was evaluated from
measurements of adsorption of nitrogen gas on alumina by
Micromeritics1 Flow-Sorb II 2300 surface area analyzer and
was found to be 165 m2/g. The point of zero charge (pzc) of
the gamma alumina is reported to be *9.1 [45]. The silica
used was synthetic precipitated silica supplied by PPG
Industries, Inc. (Pittsburgh, PA) as Hi-Sil1 255. The surface
area of this silica, as measured in this laboratory using the
method described above, is 127 m2/g. The pzc of the syn-
thetic precipitated silica is reported to be between 2 and 3.5
[45]. Both the adsorbents were used without further purifi-
cation. The NaCl used was obtained from EM Science
(Gibbstown, NJ) and was greater than 99% purity. Distilled
and deionized water of Millipore quality (resistivity
*18 MX cm–1, pH = 5 ± 1) was used in all experiments
and for the preparation of the stock NaCl and surfactant
solutions. Methanol was obtained from Fisher (Fairlawn, NJ)
at 99.9% purity and was used in all cleaning procedures.
Methods
Precipitation phase boundaries of anionic and cationic
surfactant mixture were approximated using the method of
Stellner et al. [2]. While precipitation is not a main focus of
this research, these approximate precipitation boundaries
provided guidance as to what surfactant mixtures should be
evaluated and/or avoided in the adsorption studies. Mixed
anionic–cationic surfactant systems were prepared in 15-
mL glass centrifuge vials (Fisher Scientific; Denver, CO)
by keeping the concentration of the anionic surfactant
constant and varying the concentration of the cationic
surfactant. The stock solutions of various surfactants and
electrolyte (NaCl) were mixed in various ratios to achieve
desired concentrations. The samples were first kept in a
refrigerator for one day at 4 C to force precipitation and
thus avoid supersaturation [2]. These vials were then
placed at room temperature (23 C) and shaken periodi-
cally for one week. The presence of precipitate in solution
was determined visually (precipitate crystals glisten in the
presence of high intensity light [2]).
For adsorption studies, surfactant systems were also
prepared in 15-mL glass centrifuge vials supplied by Fisher
Scientific (Denver, CO). The volume of surfactant solution
was kept constant at 10 mL. The concentration of the
individual surfactant component or of the mixture was
varied from 10–6 M to 1 M. Initial surfactant concentra-
tions were analytically measured (described later in this
section) to maximize accuracy. Adsorption experiments
were carried out at a constant temperature of 30 C by
putting the vials in a water bath. Hydrochloric acid and
sodium hydroxide were used for adjusting pH in the sur-
factant solutions. The sample pH was kept constant at
6 ± 0.5. For adsorption studies, the amount of alumina
added was sufficient to significantly decrease the initial

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concentration while making sure that the final surfactant
concentrations were detectable. The amount of adsorption
was quantified by mass balance using the following
formula:
ðCi  Cf ÞV
C¼ ð1Þ
m these systems to precipitate and/or form liquid crystals. To
where C is the surfactant adsorption in mmol/g, Ci is the
initial surfactant concentration (mmol/L), Cf is the final
surfactant concentration (mmol/L), V is the volume of
sample (L) and m is the mass of adsorbent (grams).
For adsorption studies, the vials were capped and put in a
Ping-PongTM (#51504-00) shaker (Cole Parmer) and mixed
at a frequency of 200 oscillations/min. The samples were
agitated for a period of 1 h. Next, the samples were thor-
oughly mixed using a vortex mixer (Maxi Mix II,
Thermolyne, Dubuque, IW) for 1 min and placed in a water
bath at 30 C for an additional day to ensure equilibrium
(equilibrium was reached in all experiments within one day
in close agreement with previous work [25]). The pH of each
sample was then measured by an OrionTM model 710A pH/
ISE meter and adjusted to 6.0; the above process was repe-
ated (usually 3–4 time) until the sample pH was 6.0 ± 0.5
after equilibration. For all the adsorption studies done in this
work with mixtures of anionic and cationic surfactants, first
the anionic surfactant (SDS or SDHS) was allowed to
equilibrate with the adsorbate for approximately one day
while keeping the pH at 6.0 ± 0.5 (in other words anionic
surfactant was pre-adsorbed on the adsorbate). After this
procedure the cationic surfactant (DPCl or BCl) was added
and allowed to equilibrate with the adsorbate and the pre-
adsorbed anionic surfactant for approximately 1 day. During
the test the pH was maintained constant at 6.0 ± 0.5.
The concentrations of anionic and cationic surfactants
were measured using high performance liquid chromatog-
raphy, HPLC (Dionex Corp., Sunnyvale, CA). Anionic
surfactants were analyzed by first coupling with tetrabutyl
ammonium hydroxide; the neutral complex was chromato-
graphically separated from the cationic surfactant in a
reverse-phase column (Dionex-NS1: Dionex Corp.). The
mobile phase consisted of water/acetonitrile (90%) and
tetrabutyl ammonium hydroxide (10%) with a total flow rate
of 1 mL/min. After the neutral surfactant complex was
eluted from the LC column it was decoupled by an ionic
suppressor and the surfactant was detected by electrical
conductivity (Dionex-CD25; Dionex Corp.). The cationic
surfactant was detected by the same method except that it
was coupled using methane sulfonic acid. The BCl was
detected by UV absorbance at 225 nm (AD25 Absorbance
Detector, Dionex Corp.). The adsorption of both anionic and
cationic component surfactants was quantified using Eq. 1
and reported as mmol of surfactant adsorbed per gram of
adsorbent.
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Results and Discussion
Precipitation Studies
A major obstacle in conducting adsorption studies of
anionic–cationic surfactant mixtures is the tendency of
define the isotropic concentration region where adsorption
studies can be carried out without precipitation occurring,
precipitation phase boundaries were identified. The pre-
cipitation phase boundaries for SDHS-DPCl, SDHS-BCl,
SDS-BCl and SDS-DPCl systems are shown in Fig. 1. The
precipitation studies were conducted in the presence of
0.15 M NaCl concentrations, which were added to make
the results comparable to previous research [2, 39]. Similar
to the results of Stellner et al. [2] and Doan et al. [39], these
systems show three different regions of the phase bound-
ary. For low concentrations of both surfactants, only
monomers are present. As the concentration of anionic
surfactant is increased, anionic rich micelles are formed,
requiring higher cationic surfactant concentrations to force
precipitation due to competition between monomer and
mixed micelles. Similarly, at higher cationic surfactant
concentration (cationic-rich micellar region), a higher
concentration of anionic surfactant is necessary for the
onset of precipitation. The monomer region, anionic-rich
micellar region and cationic-rich micellar region are shown
in Fig. 1. While the precipitation studies in this work were
done at 23 C and the adsorption experiments were per-
formed at 30 C, the precipitation phase diagrams provided
conservative guidance for where to conduct the adsorption
studies since the precipitation phase diagrams at 30 C will
be even smaller than what was reported at 23 C [46]. In
addition, the absence of precipitation during adsorption
experiments was corroborated by visual observation.
Fig. 1 Precipitation phase boundaries of SDHS-DPCl, SDHS-BCl,
SDS-BCl and SDS-DPCl*, anionic–cationic surfactant systems at
23 C, and in the presence of 0.15 M NaCl. *Adapted from reference
2 (30 C)
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The data in Fig. 1 demonstrate the relative tendency of
various anionic and cationic systems to precipitate. The
smallest precipitation region is observed for the most
asymmetric system (i.e., when both the anionic and cat-
ionic surfactants are branched—the SDHS-BCl system).
For the SDHS-DPCl system, where SDHS is branched and
DPCl is linear, and for SDS-BCl surfactant systems, where
SDS is linear and BCl is branched, the precipitation region
is larger than for SDHS-BCl. The largest precipitation
region occurs for the mixture containing the most sym-
metric surfactant combination (i.e. the linear–linear SDS-
DPCl system). These results are consistent with the
expectation that surfactant tail asymmetry and branching
will reduce the head–head interactions between anionic and
cationic surfactants and thus the tendency of the mixed
surfactant system to form structured precipitate phases
[47].
Adsorption Enhancement Studies
The first objective of this work was to evaluate how sur-
factant adsorption is affected when adding a cationic
surfactant to systems of pre-adsorbed anionic surfactant on
alumina. Figure 2a illustrates the adsorption isotherm for
anionic surfactant alone and anionic–cationic surfactant
mixtures onto alumina [24], where the log of the surfactant
adsorption on alumina is plotted versus the log of the
equilibrium aqueous surfactant concentration. At the pH
evaluated (pH = 6.0 ± 0.5), the alumina is positively
charged (alumina has a pzc of *9.1); conversely silica is
negatively charged at pH = 6.0 ± 0.5, since its pzc is *3.
As can be seen from the SDS-alone adsorption isotherm on
alumina (Fig. 2a), four distinct adsorption regions exist
when an anionic surfactant adsorbs onto a positively
Fig. 2 Adsorption isotherms of SDS-DPCl and SDS-BCl systems
with fixed initial concentration of DPCl (DPClo) and BCl (BClo): a
SDS adsorption isotherms with (i) DPClo = 5 · 10–6 M, (ii)
DPClo = 10–6 M, (iii) BClo = 1.75 · 10–5 M and (iv) SDS alone,
273
charged mineral oxide surface. Region I adsorption occurs
at low equilibrium surfactant concentrations and is known
as Henry’s law adsorption region. The surfactant molecules
adsorb individually and linearly in this region with minimal
lateral interactions between adsorbed surfactants [23, 26].
With increasing surfactant concentration, the slope of
the adsorption isotherm increases sharply at the critical
admicelle concentration (CAC, see Fig. 2a), which marks
the onset of Region II adsorption. The surfactant adsorbed
in Region II forms ‘‘micelle-like’’ aggregates or admicelles
[48] on the solid surface. The surface aggregates form due
to the hydrophobic interaction between the tail groups of
the bilayered adsorbed surfactant molecules. Region III is
characterized by a decrease in isotherm slope relative to the
slope in Region II. This change in slope can be attributed to
lateral electrostatic repulsion between surfactant molecules
and/or surface site heterogeneities. Region IV is the plateau
adsorption region, which commences at the CMC of the
surfactant system. At the CMC, the concentration of the
surfactant monomer becomes constant and consequently no
further adsorption occurs at higher surfactant concentra-
tions. It should be noted that this plateau adsorption may
not reflect complete surface bilayer coverage.
In addition to adsorption of SDS alone, the co-adsorp-
tion of either DPCl or BCl with pre-adsorbed SDS was also
investigated. All adsorption studies of mixed anionic–cat-
ionic surfactant systems were performed such that
equilibrium concentrations of anionic and cationic surfac-
tants were in the monomer-only region of the precipitation
phase boundary (i.e., below the CMC). It was observed
that, for the same equilibrium SDS concentration (e.g.,
10–5 M), the SDS adsorption on alumina increased when
DPCl and BCl were added to the system (Fig. 2a).
Figure 2a also indicates that the SDS adsorption further
increased as a yet higher DPCl concentration was added
on alumina; b Adsorption isotherms of (i) SDS plus DPCl,
DPClo = 5 · 10–6 M, (ii) SDS plus BCl, BClo = 1.75 · 10–5 M
and (iii) SDS alone, on alumina. All experiments were performed in
the presence of 0.02 M NaCl and at pH = 6.0 ± 0.5 and at 30 C
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Fig. 3 Adsorption isotherms of SDHS-DPCl and SDHS-BCl sys-
tems with fixed initial concentration of DPCl (DPClo) and BCl
(BClo): a SDHS adsorption isotherms with (i) DPClo = 10–5 M, (ii)
BClo = 10–5 M and (iii) SDHS alone, on alumina; b Adsorption
(5 · 10–6 M versus 10–6 M). These results confirm our
hypothesis that surfactant adsorption can be enhanced by
adding a cationic surfactant to a pre-adsorbed anionic
surfactant-alumina system. It is also interesting to note that
the SDS adsorption enhancement caused by 5 · 10–6 M
DPCl is greater than that caused by addition of *3 times
more BCl (1.75 · 10–5 M), which indicates a higher syn-
ergism of SDS adsorption for the SDS-DPCl system than
for the SDS-BCl system.
For interpretation of these results, the conceptual model
is proposed that as cationic surfactants adsorbs between the
anionic surfactants, they reduce the electrostatic repulsion
between the similarly charged head groups. This reduction
in lateral repulsion allows closer packing of the anionic
surfactant, thus accounting for the increase in SDS
adsorption observed in Fig. 2a. This increased adsorption
could also be due to increased coverage of adsorption sites
not filled when the plateau adsorption was achieved. The
greater asymmetry (branching) of the SDS-BCl system
reduces the amount of adsorption synergism versus the
SDS-DPCl system (linear-branched versus linear–linear
system respectively). In Fig. 2b, the total (i.e.,
SDS + cationic) surfactant adsorption is plotted versus the
total (SDS + cationic) aqueous surfactant concentration.
By comparing Fig. 2a and b one can observe that both the
cationic and anionic surfactants participate in the adsorp-
tion. This enhancement is especially noticed at low anionic
surfactant concentrations where the ratio of cationic sur-
factants to anionic surfactants is high. For higher
concentrations of SDS, the increase in adsorption caused
by the relatively lower concentration of cationic surfactant
is less significant and the curves of total adsorption and
SDS adsorption approach one another.
From Fig. 3a the adsorption of SDHS alone once again
shows four characteristic regions of adsorption. Figure 3a
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isotherms of (i) SDHS plus DPCl, DPClo = 10–5 M, (ii) SDHS plus
BCl, BClo = 10–5 M and (iii) SDHS alone, on alumina. All
experiments were performed in the presence of 0.02 M NaCl and
at pH = 6.0 ± 0.5 and at 30 C
also demonstrates that addition of cationic surfactants
below the CMC increases the adsorption of the anionic
surfactant, SDHS. The increased adsorption is observed to
be similar for both BCl and DPCl, suggesting a similar
extent of synergism between these two cationic surfactants
and the branched SDHS.
Adsorption of Surfactants on liked, charged surface
The second objective of this work was to demonstrate that
cationic surfactants will co-adsorb on positively charged
surfaces when anionic surfactants are present and vice
versa. Figure 4 shows the co-adsorption of increasing
concentrations of DPCl added to a constant initial con-
centrations of SDS (SDSo = 0.02 M) with positively
charged alumina. It can be seen that, in the presence of
initially pre-adsorbed SDS on alumina, DPCl also adsorbed
on alumina and the amount of DPCl adsorption increased
with increasing concentrations of DPCl added. Thus, while
the cationic surfactant DPCl does not adsorb by itself on
positively charged alumina, it does co-adsorb with the
anionic surfactant SDS. While the DPCl adsorption
increased with increasing DPCl concentration, the SDS
adsorption remained relatively constant with increasing
DPCl concentration (Fig. 4).
To understand these SDS-DPCl adsorption results,
consider that the SDS is initially adsorbed on the alumina
surface. Since the final concentration of the SDS solution is
above the CMC, and comparing the plateau adsorption
level (at the CMC) to the adsorption level at the Region I to
Region II transition (CAC), the vast majority of the
adsorbed surfactant is expected to exist on surface patches
as admicelles rather than on less energetic patches as un-
aggregated adsorbed molecules. The spacing of the
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Fig. 4 Adsorption of DPCl and SDS on 0.15 g of alumina from a

mixed solution of DPCl and SDS with constant initial SDS
concentration of 0.02 M. Both experiments were performed at Fig. 5 Adsorption of DPCl and SDHS on 0.5 g of alumina from a
pH = 6 ± 0.5 and at 30 C mixed solution of DPCl and SDHS with constant initial SDHS
concentration of 0.1 M. Both experiments were performed at
pH = 6 ± 0.5 and at 30 C
negatively charged SDS headgroups in pre-adsorbed ad-
micelles is determined by electrostatic repulsion. These
anionic headgroups provide an attractive location for the
co-adsorption of positive DPCl head groups. In addition to
the favorable electrostatic interactions between the oppo-
sitely charged headgroups, there are also favorable
hydrophobic interactions between the tails of the DPCl and
SDS molecules. All these interactions lead to co-adsorption
of cationic surfactants along with SDS on the alumina, and
thus increased packing density of surfactant on the surface.
It is interesting to note from Fig. 4 that as the DPCl
equilibrium aqueous concentration increases the amount of
adsorbed DPCl approaches the amount of adsorbed SDS;
i.e., the adsorbed surfactant approaches a 1:1 ratio. It is also
interesting to note that, by extrapolation, it appears that this Fig. 6 Adsorption of BCl and SDHS on 0.5 g of alumina from a
1:1 ratio of adsorbed surfactant would occur when the mixed solution of BCl and SDHS with constant initial SDHS
aqueous SDS and DPCl concentrations become similar; concentration of 0.1 M. Both experiments were performed at
pH = 6 ± 0.5 and at 30 C
precipitation prevented us from studying this case.
Similar trends were observed for the adsorption of
SDHS-DPCl (Fig. 5) and SDHS-BCl (Fig. 6) mixtures on
alumina with constant initial concentration of SDHS
(SDHSo = 0.1 M) at pH = 6.0 ± 0.5; that is, increasing
amounts of DPCl or BCl adsorption were observed while
the adsorption of SDHS remained relatively constant with
increasing concentration of the cationic surfactant.
Analogous trends were obtained for the adsorption of DPCl
rich SDS-DPCl mixtures on negatively charged silica
(pH = 6.0 ± 0.5) where the concentration of DPCl was
kept constant at 0.1 M while that of SDS was varied from
10–5 M to 10–2 M (Fig. 7). Ninness et al. [49] likewise
observed that for CTAB-SDS mixed surfactant adsorption
on TiO2, adsorption of SDS was achieved on negatively
charged TiO2 in the presence of pre-adsorbed CTAB. All Fig. 7 Adsorption of SDS and DPCl on 0.3 g of silica from a mixed
solution of SDS and DPCl with constant initial DPCl concentration of
of these results demonstrate that the adsorbed surfactant 0.1 M. Both experiments were performed at pH = 6 ± 0.5 and at
approached a 1:1 ratio as the aqueous concentration of the 30 C

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cationic surfactant approaches that of the anionic
surfactant.
Adsorption Reduction Studies
For certain applications, surfactant adsorption is undesir-
able. For example, in enhanced oil recovery and soil
remediation, surfactant adsorption on solid surfaces can
reduce the surfactant activity in solution and thus result in
decreased performance. The third objective of this work
was to demonstrate that it is possible to minimize surfac-
tant adsorption onto oppositely charged surfaces by using
anionic–cationic mixtures above the CMC. The hypothesis
assumed that in a mixture of anionic and cationic surfac-
tants, if the supra-CMC mixture is rich in anionic
surfactant then cationic surfactants will be ‘‘sequestered’’
in the anionic-rich micelles and adsorption of the cationic
surfactant onto negatively charged surfaces will be mini-
mized. Similarly, in a cationic-rich mixed micellar system,
anionic surfactants will be ‘‘sequestered’’ in cationic-rich
micelles and its adsorption on positively charged surfaces
such as alumina will be diminished.
To test this hypothesis, the adsorption of anionic sur-
factants from cationic-rich micellar systems and cationic
surfactants from anionic-rich micellar systems on alumina
and silica were studied, respectively. In these studies the
anionic and cationic surfactants were mixed before
adsorption (i.e., these studies used virgin surfaces, or sur-
faces without pre-adsorption). The systems evaluated were
selected to avoid precipitation by being either in the cat-
ionic-rich micellar region or in the anionic-rich micellar
region of the precipitation phase diagram. It was observed
that when the SDHS is present in BCl rich system, the
differences between concentrations of SDHS before and
after adsorption were very small (\1 to 2% on average),
which is less than typical variations in HPLC measure-
ments (*5%). It was, therefore concluded that negligible
adsorption of SDHS and BCl took place on alumina.
These results are consistent with the hypothesis that,
when present in low concentrations, anionic surfactants
will predominantly exist in cationic-rich micelles and thus
be unavailable for adsorption. And since the BCl only
adsorbs on alumina by co-adsorbing with the SDHS,
when the adsorption of SDHS is minimized or eliminated
on alumina, the BCl adsorption will likewise be mini-
mized or eliminated on alumina. Similar results were
obtained for adsorption of SDHS-DPCl and SDS-DPCl
mixtures on alumina where DPCl-rich micelles existed.
The above results confirm the hypothesis that low con-
centrations of anionic surfactants, when present in a
cationic-rich micellar system, will have negligible
adsorption on positively charged surfaces such as
123
J Surfact Deterg (2007) 10:269–277
alumina. Similar results were also obtained for the
adsorption of SDS-rich SDS-DPCl mixtures on negatively
charged silica (i.e., negligible adsorption of either sur-
factant component was observed).
Acknowledgments Financial support for this work was provided by
industrial sponsors of the Institute for Applied Surfactant Research,
University of Oklahoma, including Akzo Nobel, Clorox, Conoco/
Phillips, Church and Dwight, Dial, Ecolab, Halliburton, Huntsman,
Kerr-McGee, Oxiteno, Procter & Gamble, Sasol, Shell Chemical, and
Unilever. In addition support was also received from Dr. David A.
Sabatini’s Sun Oil Company Chair and Dr. John F. Scamehorn’s
Asahi Glass Chair.
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Author Biographies
Anand Upadhyaya received his B.Tech. in Chemical Engineering
from Indian Institute of Technology, Mumbai, India, and his M.Sc. in
Chemical Engineering from University of Oklahoma. He is currently
Formulation Chemist at Nanofilm Ltd, Valley View, Ohio. His work
focuses on the development of surfactant based consumer products.
Edgar J. Acosta received his B.Sc. in Chemical Engineering from
the Universidad del Zulia (Venezuela) in 1996, and his M.Sc. and
Ph.D. in Chemical Engineering from the University of Oklahoma in
2000 and 2004, respectively. He is currently an assistant professor at
the department of Chemical Engineering of the University of Toronto.
His research encompasses the area of colloids, complex fluids and
formulation engineering.
John F. Scamehorn holds the Asahi Glass Chair in Chemical
Engineering and is Director of the Institute for Applied Surfactant
Research at the University of Oklahoma. He received his B.Sc. and
M.Sc. at the University of Nebraska and his Ph.D. at the University of
Texas, all in chemical engineering. Dr. Scamehorn has worked for
Shell, Conoco, and DuPont and has been on a number of editorial
boards for journals in the area of surfactants and of separation science.
He has edited four books and coauthored over 170 technical papers.
His research interests include surfactant properties important in
consumer product formulation and surfactant-based separation
processes.
David A. Sabatini is David Ross Boyd Professor and Sun Oil
Company Chair of Civil Engineering and Environmental Science and
is Associate Director of the Institute for Applied Surfactant Research
at the University of Oklahoma. He received his B.Sc. from the Uni-
versity of Illinois (1981), his M.Sc. from Memphis State University
(1985), and his Ph.D. from Iowa State University (1989). His research
interests include surfactant-based microemulsion systems for con-
sumer products, environmental remediation and replacement of
organic solvents.
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