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Sodium Lauryl Ether Sulfate Micellization and Water Solubility Enhancement

Towards Naphthalene and Pyrene: Effect of the Degree of Ethoxylation

Article  in  Journal of Surfactants and Detergents · May 2010

DOI: 10.1007/s11743-009-1131-9

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J Surfact Deterg (2010) 13:103–111
DOI 10.1007/s11743-009-1131-9
ORIGINAL ARTICLE
Sodium Lauryl Ether Sulfate Micellization and Water Solubility
Enhancement Towards Naphthalene and Pyrene: Effect
of the Degree of Ethoxylation
Mohamed Aoudia Æ Butheina Al-Haddabi Æ
Zuleikha Al-Harthi Æ Aadel Al-Rubkhi
Received: 2 April 2009 / Accepted: 13 April 2009 / Published online: 19 May 2009
Ó AOCS 2009
Abstract The effect of ethoxylation on self-aggregation
behavior in aqueous media of sodium lauryl ether sulfate
(SLES), C12H25 (OCH2CH2)xOSO3Na, where x = 1
(SLE1S), x = 2 (SLE2S), and x = (SLE3S) was inves-
tigated. CMCs were determined from the effect of
surfactant concentration on (2,20 -bipyridine dichloro-
ruthenium(II) hexahydrate (Ru(bipy)2? -
3 ,2Cl ) fluorescence
emission. Aggregation numbers and micelle concentra-
tions were estimated from the fluorescent quenching of
(Ru(bipy)2? -
3 ,2Cl ) by 9-methylanthracene. Interestingly,
critical micelle concentrations (0.80 mM), average
aggregation numbers (N = 43), and micelle concentra-
tions ([M] = 40 lM) were found to be independent of the
degree of ethoxylation. Water solubilization enhancement
of naphthalene and pyrene by SLES was also investi-
gated. Water solubility enhancement for naphthalene and
pyrene was observed with increasing degrees of ethoxy-
lation and follow the order SLE3S [ SLE2S [ SLE1S.
The higher impact of oxyethylene (OE) groups on solu-
bilization enhancement of naphthalene over pyrene was
taken as an indication for a preferential distribution of the
relatively polar organic naphthalene molecule at the outer
layer of the micelle in close contact with the hydrated
oxyethylene units, thereby allowing for a strong polycy-
clic aromatic hydrocarbon (PAH)—micelle interaction.
On the other hand, pyrene molecule is preferentially
distributed in the core of the micelle, relatively far away
from the OE units located at the micelle-water interface
for PAH-micelle interaction to occur. Water solubility
enhancement for both PAHs was also was associated with
M. Aoudia (&)
B. Al-Haddabi
Z. Al-Harthi
A. Al-Rubkhi
College of Science, Sultan Qaboos University, P.O. Box 36,
Al-Khoodh, Muscat 123, Sultanate of Oman
e-mail: aoudia@squ.edu.om
an increase in SLES micelle size with the degree of
ethoxylation as well as to the accessibility of the locus
solubilization for the solute.
Keywords Micelle
Solubilization

Degree of ethoxylation
Aggregation number

Fluorescence quenching
Introduction
Contamination of soil and underground water by polycy-
clic aromatic hydrocarbons (PAHs) is a global environ-
mental concern. Because of their very hydrophobic
character and low aqueous solubility [1] (for example,
32.5 ppm for naphthalene and 0.14 ppm for pyrene), PAHs
strongly adsorb on to soil sediments making them persist in
the soil for extended periods of time. As a result, remedi-
ation of PAHs in soil-water systems requires a two-step
process that involves desorption of the contaminant from
the solid surface and micropores into the bulk aqueous
phase. Once in the bulk aqueous phase, different treatment
systems (such as bioremediation) may be used to achieve
remediation [2]. It is therefore essential to enhance water
solubility of PAHs for the successful remediation process.
One promising technique, surfactant-enhanced subsurface
remediation has emerged in which the solubility of the
organic solute is greatly enhanced by the presence of sur-
factant micelles [3–5]. In this technique, the apparent sol-
ubility of otherwise slightly water-soluble PAH can be
drastically enhanced in solutions at surfactant concentra-
tions above the critical micelle concentration (CMC),
where each micelle can accommodate a certain amount of
PAH compounds in its hydrophobic core and/or at the
solvent-micelle interface.
123
104
Most of the work conducted on surfactant-aided reme-
diation of PAHs focused on the use of nonionic surfactants
[6–10], whereas only a limited number of investigations
reported on the solubilization enhancement of PAHs by
anionic surfactants [11, 12]. This is mainly justified by:
(1) the relatively low solubilization power of anionic micelles
compared to that of nonionic micelles, owing to the high
critical micelle concentration (CMC) often displayed by
anionic surfactants; and (2) the high tolerance of nonionic
surfactants to electrolytes. However, the effectiveness of a
surfactant-enhanced remediation process can be harmed by
surfactant adsorption onto soil and/or precipitation with
natural hardness in groundwater. Anionic surfactants are
certainly more resistant to adsorption onto sandy and clay
soils than nonionic surfactants, due to the strong electro-
static repulsion between anionic surfactants and negatively
charged surfaces. On the other hand, the negatively
charged head group of anionic surfactants makes them
more vulnerable to precipitation losses [13].
In order to combine the favorable properties of both
anionic surfactants (low adsorption onto soils) and non-
ionic surfactants (compatibility with the underground water
hardness), we proposed to investigate water solubilization
enhancement of two PAH model components having dif-
ferent polarity (naphthalene and pyrene) by a series of
sodium lauryl ether sulfate (SLES) surfactants with dif-
ferent degree of ethoxylation, C12H25–(OC2H4)x–OSO3Na,
with x = 1 (SLE1S), x = 2 (SLE2S), and x = 3 (SLE3S).
This choice was based on the knowledge that: (1) naph-
thalene and pyrene have may be solubilized in two dif-
ferent micelle environments, namely the water-micelle
interface and the micellar core [14] and (2) sodium lauryl
ether sulfates showed high hydrocarbon solubilization
potential while exhibiting low losses in the substrate due to
precipitation or adsorption onto soils which may harm the
remedial process [13]. Our choice for this particular class
of surfactants (ethoxylated anionic surfactants) was also
motivated by the fact that in spite of their wide range of
applications, their self-aggregation in aqueous solutions is
not clearly understood. For instance, it may be anticipated
that the addition of hydrophilic oxyethylene (OE) groups
adjacent to the anionic sulfate moiety would increase the
overall hydrophilic character of the molecule and increase
the CMC accordingly. In fact, the critical micelle con-
centration of SLE1S, SLE2S, and SLE3S were measured
by different methods and were found to be all similar
(*0.80 mM) [12, 15] significantly lower than the CMC of
the analogous nonethoxylated counterpart (sodium dodecyl
sulfate, CMC = 8.2 mM). This unexpected behavior
was attributed by Sowada [16] to the hydrophobic
character of the oxyethylene (OE) groups linked to sulfate
ion (–OSO3-). Sowada calculated the effective carbon
number and methylene group equivalent values for 32 alkyl
123
J Surfact Deterg (2010) 13:103–111
ether sulfates containing 1–10 (OCH2CH2) groups per
molecule. The oxyethylene group in these alkyl ether
sulfates was found to have a lipophilic character. Hydro-
phobic-lipophilic balance values (HLB) were estimated
and were found to differ from the generally accepted values
of ?0.33, valid only for nonionic surfactants. Only very
recently, have we showed [15] that similar CMCs
(0.8 mM) observed for the three ethoxylated surfactants
can be attributed to intermolecular and intermolecular ion-
dipole attractive interactions involving the sulfate ion
(–OSO3–) and the O ? CH2 dipole of the oxyethylene
(OE) group in SLES micelles. The objective of this work
was therefore three-fold: (1) investigate the effect of the
degree of ethoxylation on SLES self-aggregation (average
aggregation number and micelle concentration) in aqueous
media; (2) evaluate the effect of the degree of ethoxylation
on water solubilization enhancement of naphthalene and
pyrene and compare with the nonethoxylated counterpart
sodium dodecyl sulfate (C12H25OSO3Na, SLE0S); and
(3) correlate the solubilization enhancement of naphthalene
and pyrene to a possible micelle structure alteration upon
increasing the degree of ethoxylation. The hypothesis
behind this research is that the observed unusual self-
aggregation properties of SLES surfactants in aqueous
media (invariance of the CMC with the degree of ethoxy-
lation) will also be reflected in their PAH solubilization
effectiveness.
Experimental Procedures
Chemicals
Naphthalene and pyrene were purchased from Fluka. The
purities of these compounds were greater than or equal to
99%. Water solubility of naphthalene and pyrene are 2.5
(10-4 and 6.4 9 10-7 M, respectively [1]. Sodium dodecyl
sulfate (SDS [99%) was obtained from the Sigma Chemi-
cals Co. Lauryl alcohol polyoxyethylene (23EO average)
alcohol (LA23EOA) was purchased from Sigma. Sodium
lauryl ether sulfates (SLES), i.e. C12H25 (OC2H4)xOSO3Na,
having different degrees of ethoxylation (x = 1 for SLE1S,
x = 2 for SLE2S, and x = 3 for SLE3S) were kindly pro-
vided by the Stepan Company. These surfactants are claimed
to be consistent, high purity products due to the continuous
sulfation process used. They were approximately 25%
active. Surfactant solutions were prepared with deionized
water (resistivity 18 lX cm). Methanol (Aldrich) used in
UV analysis was HPLC grade of greater or equal to 99%
purity. Tri(2,20 -bipyridylchloro-ruthenium(II) hexahydrate
(99.5%) and 9-methylanthracene ([98%) used in this study
were purchased from Aldrich. All experimental measure-
ments were carried out at room temperature (23 °C).
J Surfact Deterg (2010) 13:103–111 105

Methods ðIo =IÞ ¼ expf½Q=½Mg ð1Þ

The procedure for solubility measurements was essentially where [M] is the micelle concentration. Thus, a semi-log
similar to that described elsewhere [17]. Surfactant solu- plot of the left-hand side of Eq. 1 against [Q] will be linear
tions were placed in 25-ml flasks at concentrations above with a slope equal to [M]-1. The surfactant mean
the CMC. An amount of each PAH in excess of its apparent aggregation number is then given by
solubility was added to each flask (crystalline PAH was N ¼ f½S  CMCg=½M ð2Þ
observed at the end of each experiment). Duplicate samples
where [S] is the total surfactant concentration.
were made for each surfactant concentration. The flasks
were placed in an orbital shaker (Gallenkemp) at 150 rpm
for 48 h in an air-conditioned room (22 °C). The samples
Results and Discussion
were then allowed to stand for about 15 h. Liquid samples
from each flask were removed and centrifuged at
Effect of the Degree of Ethoxylation on SLES
1,500 rpm for 30 min before analysis. The determination
Self-Aggregation
of PAH concentration was done by UV absorption (HP 845
X spectrophotometer). A 1-ml amount of the supernatant
We measured the critical micelle concentrations of three
surfactant solution was placed in a 10-ml volumetric flask
SLES (SLE1S, SLE2S, and SLE3S) using the effect of the
and diluted by methanol to the mark (methanol 90%/
surfactant concentration on Ru(bipy)2? 3 fluorescence
deionized water 10%). The absorbance was detected at
emission. This fluorescence was observed to be very sen-
276 nm for naphthalene and 334 nm for pyrene. Calibra-
sitive to the surfactant concentration, probably due to the
tion curves were prepared for naphthalene and pyrene with
strong electrostatic interaction between the positively
standard solutions by dissolving the aromatic solutes in
charged fluorescent probe and the negatively charged
UV-blank solvent (methanol 90%/deionized water 10%).
hydrophilic groups of the anionic surfactant [17]. Typical
Critical micelle concentrations (CMCs) were deter-
plots of kf,max (wavelength at maximum fluorescence
mined from the effect of surfactant concentration on the
emission) and If,max (maximum fluorescence intensity) with
fluorescence of 2,20 -bipyridine dichloro-ruthenium(II)
surfactant concentration are shown in Fig. 1 for SLE2S
hexahydrate (Ru(bipy)2? -
3 ,2Cl ) used as an extrinsic probe.
surfactant. As clearly seen in this Figure, both plots display
Aggregation numbers (N) and micelle concentration ([M])
an abrupt change at a similar surfactant critical micelle
were determined from fluorescence quenching of (Ru(bi-
concentration (*0.8 mM). Similar results were obtained
py)2? -
3 ,2Cl ) by 9-methylanthracene at a fixed surfactant
for SLE1S and SLE3S and are shown in Table 1. These
concentration above its CMC. Working solutions were
prepared by keeping the fluorescent probe and the quencher
concentration at 20 and 10 lM, respectively. Because of
300
the low water solubility of 9-methylanthracene, a small
volume (10 lL) of 9-methylanthracene solution in ethanol
620
was added to 10 mL working solution. This volume of 280
615
ethanol added was small enough (0.1% of the total volume)
λ f,max

610
so that the solvent did not have any effect on the micelle 260
I f,max

605
system investigated. From these solutions, the fluorescence
600
emission spectra were taken using an excitation wave-
240
length of 450 nm and CMC were extracted from the plots 595
0.0000 0.0004 0.0008 0.0012 0.0016

of kf,max (wavelength at maximum fluorescence emission) Surfactant Concentration (M)

and If,max (maximum fluorescence intensity) versus sur- 220

factant concentration.
Micelle concentration ([M]) and aggregation number (N)
200
were derived from the fluorescence quenching of the
fluorescent probe (Ru(bipy)2? 3 ) by 9-methylanthracene at 0.0000 0.0004 0.0008 0.0012 0.0016
different quencher concentrations, keeping the probe and Surfactant Concentration (M)
surfactant concentrations fixed. By assuming static
quenching and a Poisson distribution of the quencher Fig. 1 Effect of surfactant concentration (SLE2S) on the fluores-
cence emission maximum intensity (If,max) for Ru(bipy)2? 3 , 2Cl
-
molecules among micelles, the measured luminescence
(20 lM). Inset: Effect of surfactant concentration on the fluorescence
intensity of the fluorescent probe in the absence (Io) and in emission maximum intensity (kf,max) for Ru(bipy)2? -
3 , 2Cl (20 lM),
the presence (I) of the quencher (Q) is given by [18] kexc = 450 nm and T = 23 °C

123
106
Table 1 Critical micelle concentration (CMC) derived from Ru(bi-
py)2? -
3 ,2Cl fluorescence at different surfactant concentrations, aver-
age aggregation number (N) and micelle concentration ([M])
determined from fluorescence quenching of Ru(bipy)2? 3 ,2Cl
-
(20 lM) by 9-methylanthracene (10 lM) at room temperature
(23 °C) and a surfactant concentration of 2.5 mM
Surfactant CMC (mM) N [M] (lM)
a a
SLE0S 8.2 64 –
SLE1S 0.79 43 39.8
SLE2S 0.78 42 40.1
SLE3S 0.80 42 40.0
a
Ref. [19]
results are in close agreement with the values we recently
reported [15], in which the CMCs were measured using
different techniques (conductivity and fluorescence
quenching of Ru(bipy)2? 3 by 9-methylanthracene). Our
CMC values are also in close agreement with those
reported elsewhere [12], using a capillary rise method.
Also included in Table 1 are the CMC and the average
aggregation number for sodium dodecyl sulfate [19]. In our
previous study [15], two unexpected interesting properties
of micellization behavior of sodium lauryl ether sulfate
surfactants in aqueous solutions were reported, namely:
(1) the significantly low CMC values (0.8 mM) displayed
by these surfactants in comparison to the analogous non-
ethoxylated counterpart (SDS, 8.2 mM), and (2) the invari-
ance of the CMC with the degree of ethoxylation. The low
CMCs were attributed to intramolecular and intermolecular
ion-dipole interactions between the sulfate ion (–OSO3-)
and the O ? CH2 dipole of the oxyethylene (OE) group in
SLES micelles. The observed invariance of the CMC with
the degree of ethoxylation was attributed to the fact that
this ion-dipole interaction is effective only with the OE
group linked to –OSO3- (intramolecular attractive inter-
action) and the sulfate group of a given surfactant in SLES
micelles with the OE group adjacent to the sulfate group of
a nearby surfactant at the micelle-water interface (inter-
molecular attractive interaction).
In addition to the important CMC concept in surfactant
dispersions, micelles are also characterized by their
aggregation number (N). This number determines the
micelle size and can significantly affects certain interfacial
phenomena such as solubilization. Thus, the fluorescence
quenching technique was also applied to SLES aqueous
micellar dispersions, using 9-methylanthracene and
2,2-bipyridine rutheneous dichloride hexahydrate as
quencher and fluorescent probes, respectively. These meet
the requirements of water-insoluble quencher and micelle-
associated probe, respectively. Hence, both quencher and
probe reside in micelle environments. Typical fluorescence
123
J Surfact Deterg (2010) 13:103–111
40
30
Fluorescence (au)
20
10
0
500 600 700 800
Wavelength/nm
Fig. 2 Effect of quencher (9-methylanthracene) concentration on the
fluorescence emission of Ru(bipy)2? 3 , 2Cl
-
(20 lM) in SLE1S
(2.5 mM) aqueous solutions: 2.5 lM (filled circles), 5 lM (open
circles), 7.5 lM (?), 10 lM (open triangles), 15 lM (open squares),
and 20 lM (-), kexc = 450 nm and T = 23 °C
quenching is shown for the SLE1S system at different
quencher concentrations and fixed surfactant and fluores-
cent probe concentrations (Fig. 2). Similar fluorescence
quenching measurements were carried out with SLE2S and
SLE3S surfactant systems. Io/I ratios were extracted from
such measurements and plots of ln(Io/I) versus [Q] are
displayed in Fig. 3. For the three surfactants investigated, a
linear variation was observed, in accord with Eq. 1.
Micelle concentration ([M]) and mean aggregation num-
bers (N) were derived from Eqs. 1 and 2 and reported in
Table 1.
Interestingly, our results show similar micelle concen-
trations ([M] = 40.0 lM) and average aggregation num-
bers (N = 43) for all the surfactants, suggesting that further
addition of OE groups to SLE1S (SLE2S and SLE3S) has
no effect on those two aggregation properties This invari-
ance, also observed for the CMCs, can also be attributed to
the fact that the intramolecular ion-dipole interaction only
involves the surfactant sulfate group and the OE group
linked to this sulfate moiety whereas the intramolecular
ion-dipole interaction may only occur between a surfactant
micelle sulfate group and the first OE group (linked to the
sulfate group) of a nearby surfactant molecule at the
micelle-water interface. Hence, at a given surfactant con-
centration, SLES (SLE1S, SLE2S, and SLE3S) micellar
dispersions are characterized by identical critical micelle
concentrations, average micelle aggregation numbers, and
micelle concentrations. Accordingly, it appears interesting
to correlate the effect of such an unexpected self-aggre-
gation behavior of SLES surfactants with their micelle
solubilization effectiveness for PAH compounds.
J Surfact Deterg (2010) 13:103–111 107

0.0007
0.6

0.0006

Pyrene Concentration (M)

0.5
0.0005
0.4
0.0004
ln(I /I)
o

0.3
0.0003

0.2
0.0002

0.1
0.0001

0.0 0.0000
0.0 0.5 1.0 1.5 2.0 0.00 0.01 0.02 0.03 0.04 0.05
Quencher Concentration (10 5 M) Surfactant Concentration (M)

Fig. 3 Variation of the fluorescence of 2,2-bipyridine rutheneous Fig. 4 Water solubilization enhancements of pyrene in different
dichloride hexahydrate (Ru(bipy)2? -
3 , 2Cl ) in the absence (Io) and the surfactant aqueous solutions: x (SLE0S), filled circles (SLE1S), filled
presence (I) of the quencher (9-methylanthracene) in SLES aqueous triangles (SLE2S), ? (SLE3S) and open diamonds (LA23EOA),
micelle dispersions: ? (SLE1S), 9 (SLE2S), and o (SLE3S). Sur- room temperature
factant concentration fixed at 2.5 mM, kexc = 450 nm, kemi =
635 nm, and T = 23 °C

Water Solubilization Enhancement of Naphthalene

and Pyrene by SLES Micelles 0.0015
Naphthalene Concentration (M)

Measurement of the effectiveness of a particular surfactant

in solubilizing a given PAH is known as the molar solu-
bilization ratio (MSR), which is defined as the number of 0.0010
moles of solute solubilized per number of moles of sur-
factant micellized. MSR can be calculated as follows [1]
MSR ¼ ðSPAH;mic  SPAH;CMC Þ=ðCSurf  CMCÞ ð3Þ
0.0005
where SPAH,mic is the apparent solubility (aqueous plus-
micelle phase solubility) of a PAH compound at a partic-
ular surfactant concentration greater than the CMC; Csurf is
the surfactant at which SPAH,mic is measured; and SPAH,CMC 0.0000
is the PAH solubility at the CMC. The MSR may be 0.000 0.005 0.010 0.015 0.020 0.025 0.030

obtained from the slope of the variation of SPAH,mic against
surfactant concentration.
Thus, water solubilization enhancement of naphthalene
and pyrene were measured in SLE1S, SLE2S, SLE3S,
SLE0S, and LA23EOA by determining the molar solubi-
lization ratio for each individual surfactant from the mea-
surement of naphthalene and pyrene solubility with
surfactant concentration. The results are shown in Figs. 4
and 5. The slopes of the different lines, which represent
molar solubilization ratios, were calculated using least-
squares linear regression and are reported in Table 1. In
general, r2 values close to 0.99 were obtained for all PAH-
surfactant systems investigated.
Inspection of Table 2 shows that MSR ratio values for
naphthalene are in close agreement with the values repor-
ted elsewhere [12, 20, 21]. On the other hand, studies on
Surfactant Concentration (M)
Fig. 5 Water solubilization enhancements of naphthalene in different
surfactant aqueous solutions: 9 (SLE0S), filled circles (SLE1S),
filled triangles (SLE2S), ? (SLE3S) and open diamonds
(LA23EOA), T = 23 °C
solubilization of pyrene by LA23EOA surfactant micelles
reported conflicting MSR values, namely 0.062 [8] and
0.038 [21]. Our MSR value (0.038) agrees with the latter.
LA23EOA surfactant was selected in this study because of
its similar hydrophobic chain (C12H25-) to the corre-
sponding one in SLES surfactants. As expected, higher
MSR values for naphthalene (0.275) and pyrene (0.038)
were obtained with the nonionic surfactant. In fact, it is
well documented that for surfactants with the same
hydrophobic chain length, the order of solubilization power

123
108 J Surfact Deterg (2010) 13:103–111

Table 2 Molar solubilization ratios (MSR) of naphthalene and pyr- oxyethylene (–OCH2CH2–) polar organic moieties located
ene by surfactant micelles at room temperature (23 °C) in the outer palisade layer of the micelle. On the contrary,
Surfactant PAHs MSR MSR (literature) because of its very hydrophobic nature and very low sol-
ubility in water, we can expect weak PAH-micelle inter-
SLE1S Naphthalene 0.094 (±0.003) 0.108a
action between the pyrene molecule and the micelle OE
SLE2S 0.110 (±0.001) 0.127a hydrophilic groups. Correlation between PAH solubiliza-
SLE3S 0.139 (±0.004) 0.143a tion enhancement and PAH-micelle interaction was indeed
LA23EOA 0.275 (±0.008) 0.270b reported by Diallo et al. [22]. The authors suggested that
SLE0S 0.065 (±0.003) 0.086a hydrogen bonding between aromatic hydrocarbons and
SLE1S Pyrene 0.013 (±0.001) – water molecules bonded to surfactant oxyethylene units in
SLE2S 0.019 (±0.001) – the outer palisade layer of the micelle may be a dominant
SLE3S 0.023 (±0.002) – mechanism for solubility enhancement. Therefore, the
LA23EOA 0.038 (±0.001) 0.038b, 0.062c increase in naphthalene MSRs with degree of ethoxylation
SLE0S 0.010 (± 0.001) 0.012d can be associated with an increase in naphthalene-OE
a
Ref. [12] interaction as the number of OE groups increase from
b
Ref. [20] x = 1 (SLE1S) to x = 3 (SLE3S). Such PAH-micelle
c
Ref. [8] interaction may not be a dominant mechanism in the case
d
Ref. [21] of pyrene and the observed solubilization enhancement is
probably related to other factors such as micelle structure
change (size and/or shape) with the degree of ethoxylation.
for hydrocarbons and polar compounds follows the order In fact, the extent to which a solute can be solubilized
nonionics [ cationics [ anionics [15]. More interesting is into a particular micelle also depends on the volume of the
the comparison between the solubilization power of a locus of solubilization within the micelle (outer portion and
conventional anionic surfactant (SLE0S) and the analogous inner core). In turn, this volume depends on the shape of
anionic SLES (SLE1S, SLE2S, and SLE3S). All surfac- the micelle which is determined by the value of the packing
tants have similar hydrophobic alkyl chain (C12H25-) and parameter Pc = Vh/lcao [14]. The amount of PAH com-
different degree of ethoxylation (x = 0–3). As seen in pound (naphthalene and pyrene) that is solubilized in SLES
Table 2, SLES micelles show higher solubilization power micelles may then be determined by the effect of the
for naphthalene and pyrene than SDS micelles. Further- degree of ethoxylation on the micelle structure (shape and/
more, water solubilization enhancement of naphthalene and or size). In our experiments, surfactant concentrations
pyrene are evidenced with increasing degrees of ethoxy- (above the CMC) were kept moderately low and one may
lation. Increase in MSR by micelles is often explained in assume that SLES micelles are spherical in shape. For such
part by the decrease in the CMC of the surfactant system. spherical micelles, the amount of solute solubilized in any
Our measured CMC values are similar for the series of location within the micelle (outer palisade layer and/or
SLES surfactants investigated (Table 1), thereby the inner core) will also increase with an increase in the vol-
increase in the MSR (in one hand) and the invariance of the ume of the micelle, i.e., with an increase of the diameter of
CMC (on the other hand) with the degree of ethoxylation the micelle. Solubilization enhancements of naphthalene
appears to suggest that other factors than the CMC are and pyrene by SLES micelles (Table 2) may therefore be
indeed affecting the solubilization process in SLES reasonably associated with an increase in the micelle size
micelles. as the degree of ethoxylation is increased from SLE1S to
Solubilization of PAHs can be both in the inner and SLE3S. Our suggestion is that successive incorporation of
outer regions of the micelles [14]. In addition, solute par- each oxyethylene group (–OCH2CH2–) from SLE1S to
titioning in the micelle was shown to depend on the PAH- SLE3S will result in an increase of the micelle size,
micelle interaction [8]. Thus, a strong interaction between thereby increasing the solvent-water interface area as well
the solute and the hydrophilic group of the surfactant will as the hydrophobic micelle core. Clearly, such an increase
favor a solute solubilization at the micelle surface. On the in the solute solubilization sites will in turn result in water
other hand, a strong interaction between the solute and the solubilization enhancement for the PAHs in the order
hydrophobic tail of the surfactant will favor a solute sol- SLE3S [ SLE2S [ SLE1S, as shown in Table 2.
ubilization in the inner core of the micelle. The higher However, the micelle size increase with increasing
solubilization capacity of SLES micelles for naphthalene ethoxylation can be induced either by an increase in the
relatively to pyrene (Table 2) may therefore be the result of mean micelle aggregation number (N) or by micelle
a strong PAH-micelle interaction between the relatively structure alteration due to changes in the relative rear-
polar organic naphthalene molecule and the surfactant rangement of the surfactant molecules in the micelle.

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J Surfact Deterg (2010) 13:103–111
Results shown in Table 1 show a similar average micelle
aggregation number (N = 43) for the entire series of SLES
surfactants (SLE1S, SLE2S, and SLE3S), with the con-
sequence being that the micelle size increase with the
degree of ethoxylation cannot be related to an increase in
the average micelle aggregation number but to a plausible
change in the micelle structure. Along the series SLE1S,
SLE2S, and SLE3S, the hydrophobic alkyl tail is kept
fixed (H25C12-) whereas the degree of ethoxylation
(–OC2H4)x- is increased from 1 to 3. Thus, as the micelle
radius is probably determined by the hydrophobic alkyl
chain (C12H25-, similar for all surfactants), more room has
to be found for the increasingly longer polar oxyethylene
(OE) chain that lies at the periphery of the micelle-water
interface. To accommodate this tendency toward crowding,
it is somewhat plausible that the surfactant polar head
groups (–OSO3- and the OE moieties) separate to greater
distances, opening up the micelle structure from a some-
what compact structure to a loose one (Scheme 1). In turn,
this will result in a concomitant increase in the volume of
the outer polar layer at the solvent-micelle interface as well
as in the volume of the micellar core (solubilization sites
for both PAHs), thereby enhancing water solubility of the
two PAH compounds. This suggested opening up of the
micelle structure is clearly supported by the observed
invariance of the critical micelle concentration (CMC), the
micelle concentration ([M]), and consequently the mean
aggregation numbers (N) with the degree of ethoxylation
(Table 1).
At this juncture, it is appropriate to return our attention
to the effect of the degree of ethoxylation on the relative
solubilization of naphthalene and pyrene. Inspection of
Scheme 1 Opening up of the
Micellar structure as the degree
of ethoxylation increases: the
micelle changes from a
somehow compact structure
(SLE1S) to a loose one (SLE3S)
with no changes in the
aggregation number
Opening up of the Micellar structure as the degree of ethoxylation increases: the
micelle changes from a somehow compact structure (SLE1S) to a loose one
(SLE3S) with no changes in the aggregation number
Lauryl tail
109
Table 2 reveals that water solubilization enhancement in
lauryl ether sulfate surfactants investigated in this work
(SLE1S, SLE2S, and SLE3S) as well as in SLE0S
micelles is higher for naphthalene than for pyrene. Molar
solubilization ratios (MSRs) for both naphthalene and
pyrene are plotted versus oxyethylene number in Fig. 6.
A linear variation is observed for the two PAHs. The ratio
R = s1/s2 = 5.17 ± 0.83, where s1 is the slope of the lin-
ear variation of the MSR with the degree of ethoxylation
for naphthalene and s2 is the corresponding slope for pyr-
ene, suggesting an average of 5–6 naphthalene molecules
being solubilized per molecule of pyrene in a given
micelle. This higher impact of degree of ethoxylation on
water solubilization enhancement of naphthalene over
pyrene may indicate a preferential distribution of the rel-
atively polar organic naphthalene molecule at the outer
palisade layer of the micelle in close contact with the
hydrated oxyethylene units, thereby allowing for strong
PAH-micelle interaction [22] and high micelle solubiliza-
tion power for naphthalene. On the other hand, because of
its relatively much higher hydrophobic nature, the pyrene
molecule is preferentially distributed in the core of the
micelle, relatively far away from the OE units located at
the micelle-water interface for PAH-micelle interaction to
occur.
Finally, in addition to the PAH-surfactant interaction
effect that surely contributes to the solubilization and dis-
tribution of the solute in the micellar phase, one may
possibly invoke the effect of the curvature of the micelle on
its solubilization capacity [14]. Solubilization of pyrene
requires the transfer of a relatively large aromatic molecule
from the bulk aqueous phase to the micellar core. Such a
Hydrophilic group Oxyethylene group (OE)
123
110
0.14
0.12
0.10
0.08
MSR
0.06
0.04
0.02
0.00
0 1 2 3
<OE>
Fig. 6 Effect of the degree of ethoxylation on water solubilization
enhancement of pyrene (filled squares) and naphthalene (filled
circles) by SLES aqueous micellar dispersions, T = 23 °C
transfer from a very polar aqueous medium to a very
hydrophobic environment may be hindered by the effect of
the curvature on the micelle solubilization capacity, due to
the considerable Laplace pressure inside the micelle that
opposes pyrene diffusion into the micellar core. On the
other hand, solubilization of naphthalene requires the
transfer of a relatively small organic polar molecule from
the bulk phase to the outer palisade layer of aqueous
hydrophilic OE chains surrounding the micellar core where
naphthalene-oxyethylene interaction may occur and con-
tribute significantly to water solubilization enhancement of
the solute. The accessibility of the micelle solubilization
site to a given solute may therefore be an additional factor
to the micelle solubilization capacity. It is quite reasonable
to speculate that the accessibility of the water-micelle
interface to naphthalene molecule is relatively facile (no
pressure-gradient is opposing the transfer of the solute from
the bulk phase the micelle-water interface), whereas the
accessibility of the micelle core to pyrene pyrene is
somehow hindered by Laplace pressure gradient across the
micelle-water interface. This will, in turn, limit pyrene
incursion in the hydrophobic core of the micelle. Finally,
one may correlate the size increase in SLES micelles with
the degree of ethoxylation to a concomitant decrease in
Laplace pressure, thereby reducing the pressure-gradient
opposing the partitioning of pyrene molecules into the core
of the micelles and enhancing water solubilization of the
PAH compound.
Acknowledgments We are very grateful for His Majesty Sultan
Qaboos for the financial support of this work (Grant: SR/SCI/CHE/
04/01).
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J Surfact Deterg (2010) 13:103–111
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Author Biographies
Dr. Mohamed Aoudia is an associate professor of chemistry in the
College of Science at Sultan Qaboos University. He received a Ph.D.
from the University of Texas at Austin. He is working on enhanced oil
recovery by chemical flooding and surfactant-based processes in the
treatment and utilization of produced oil field water and contaminated
underground water.
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111
Butheina Al-Haddabi received her B.Sc. and M.Sc. from Sultan
Qaboos University. She is interested in water solubilization
enhancement of polycyclic aromatic hydrocarbons. She is currently
working at the Royal Court Affairs (Oman).
Zuleikha Al-Harti received her B.Sc. and M.Sc. from Sultan Qaboos
University. She is interested in enhanced oil recovery by surfactant
flooding as well as surfactant-rock interactions. She is currently
working in the Ministry of Education (Oman).
Aadel Al-Rubkhi received his M.Sc. from Sultan Qaboos University.
He worked as research assistant at SQU. Currently, he is working in
Methanol Plant (Salalah, Oman) as an Engineer.
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