Environ. Sci. Technol.

2001, 35, 2341-2346

Removal of Phenols from Aqueous

Streams by the Cloud Point
Extraction Technique with
Oxyethylated Methyl Dodecanoates
As Surfactants
KATARZYNA MATERNA,
IZABELA MILOSZ, IRENEUSZ MIESIAC,
G E R A R D C O T E , * , A N D
JAN SZYMANOWSKI
Poznan University of Technology, Institute of Chemical
Technology and Engineering, Pl. Sklodowskiej-Curie 2,
60-965 Poznan, Poland, and Ecole Nationale Superieure de
Chimie de Paris, Laboratoire dElectrochimie et de Chimie
Analytique (UMR CNRS-ENSCP 7575 and UPR-CECM 2801),
11, rue Pierre et Marie Curie, 75005, Paris, France

New oxyethylated methyl dodecanoates with average

degrees of oxyethylation (n) ranging between 5 and 14
(denoted OMD-n) were considered as nonionic surfactants
for the removal of phenol, 4-methylphenol, and 4-nitrophenol
from aqueous streams by the cloud point extraction
technique. The cloud point (denoted CP) strongly increases
with the average degree of oxyethylation n but is
independent of OMD-n concentration, except at low
concentration (i.e., <10 gL-1). CP can be related to the
surfactant hydrophilicity by the following equation:
CP(C) ) 20.27 HLBG - 245.8 (above 10 gL-1 and in
the absence of electrolyte), where HLBG refers to the OMD-n
hydrophile-lipophile balance in Griffins scale. The
presence of electrolyte such as NaCl strongly decreases
the cloud point [CP/[NaCl] -(9 ( 1) CM-1]. Many
parameters influence the extraction of phenols in OMD-nrich phases, including the characteristics of phenols
(hydrophobicity, hydrogen-bond acidity, hydrogen-bond
basicity, etc.), the average degree of oxyethylation of OMD-n
(i.e., n), the concentration of electrolyte, the settling
temperature (Tset), and overheating (T ) Tset - CP). The
distribution coefficients typically range between 20 and
100. Finally, the kinetics of the separation process is limited
by the slow coalescence of the fine droplets of surfactantrich phase formed above CP.

Introduction
Nowadays there is a strong concern to protect the environment, and despite major progresses achieved over the last
three decades in the field of separation techniques, the
removal of pollutants from aqueous industrial streams and
wastewaters remains an important challenge. For instance,
the conventional liquid-liquid extraction can be used to
eliminate both organic and inorganic pollutants from aqueous solutions (1), but this technique exhibits important
* To whom correspondence should be addressed. Phone and fax:
+33 1 43 25 18 76; E-mail: cote@ext.jussieu.fr.
Poznan University of Technology.
Ecole Nationale Superieure de Chimie de Paris.
10.1021/es000025y CCC: $20.00
Published on Web 04/20/2001

2001 American Chemical Society

limitations and drawbacks. In particular, the diluents and

extractants which constitute the organic solvents in which
the pollutants are extracted are slightly soluble in the aqueous
phases (2) and may be the source of an induced pollution.
As a result, new separation methods based on innovative
concepts should be developed. In this perspective, the
concept of one-phase systems, free from any organic diluent
and extractant, attracts an increasing attention. Thus, the
technique of micellar enhanced ultrafiltration (MEUF) based
on the coupling of micellar extraction and ultrafiltration was
proposed and found to be promising for water cleanup
(3-11).
Another promising method of separation also based on
the concept of one-phase systems is the cloud point extraction
technique. The cloud point phenomenon occurs when
micellar solutions of nonionic or zwitterionic surfactants are
heated. It corresponds to the fact that above a given
temperature the micellar solutions split into two liquid
phases: an almost micelle-free dilute solution of the nonionic
surfactant and a surfactant-rich phase (12). From a physical
point of view, the increase of temperature provokes the
dehydration of the hydrophilic groups of the surfactant
molecules, an increase of the aggregation number and the
swelling of the micelles until the micellar solution becomes
turbid and the separation of the surfactant-rich phase takes
place. This phenomenon is reversible and was tentatively
used to achieve the separation of different solutes (13-18).
However, in most cases, only classical oxyethylated alkyl
phenols were used as nonionic surfactants because such
compounds are easily available, exhibit appropriate physicochemical properties and can be conveniently monitored
by UV-vis spectrometry. Unfortunately, the use of oxyethylated alkyl phenols is not acceptable in the aimed application
because the latter are toxic and rather resistant to biodegradation. Furthermore, their biodegradation, as far as it takes
place, gives toxic phenol derivatives and other toxic metabolic
residues. To overcome such difficulties, the classical oxyethylated alkyl phenols can be replaced by oxyethylated
methyl carboxylates. These new surfactants which attract
much attention can be obtained by direct oxyethylation of
methyl esters of fatty acids according to eq 1 (19-24):

As they are esters, the oxyethylated methyl carboxylates

hydrolyze easily to give nontoxic and nonsurface active
moieties, i.e., fatty acids and monoethylpolyglycols. The fatty
acids can be neutralized and precipitated as their calcium
or magnesium salts, whereas the monoethylpolyglycols will
undergo the process of biodegradation further. As a result,
these new nonionic surfactants are much friendlier to the
environment than the oxyethylated alkyl phenols.
The aim of the present work was to study the removal of
organic pollutants from aqueous streams by the cloud point
extraction technique with oxyethylated methyl dodecanoates
as nonionic surfactants. Phenol, 4-methylphenol, and 4-nitrophenol were chosen as model pollutants.

Experimental Section
Reagents. Phenol, 4-methylphenol, and 4-nitrophenol of
purum quality were from LOBA CHEMIE (Austria), The British
Drug Houses Ltd. (England) and POCH (Poland), respectively,
and used as delivered. The various oxyethylated methyl
dodecanoates used were kindly provided by the Institute of
Heavy Organic Synthesis, Kedzierzyn-Kozle (Poland) and are
VOL. 35, NO. 11, 2001 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

2341

TABLE 1. Composition (wt %) of OMD-5, OMD-10, and OMD-14

components

OMD-5

individual oxyethylated methyl dodecanoates (23)

C11H23CO(OCH2CH2)nOCH3
n ) 0 (starting material)
n)1
n)2
n)3
n)4
n)5
n)6
n)7
n)8
n)9
n ) 10
n ) 11
n ) 12
n ) 13
n ) 14
n ) 15
n ) 16
n ) 17
monomethyl ethers of polyoxyethylene glycols
CH3(OCH2CH2)mOH
didodecanoates of polyoxyethylene glycols
C11H23CO(OCH2CH2)pOOC11H23

(2)

with
17

COMD-n )

[C

11H23CO(OCH2CH2)jOCH3]

j)1

and kn ) 2.24 10-3, 2.10 10-3, 2.04 10-3, 1.83 10-3,

1.62 10-3, 1.56 10-3, and 1.27 10-3 for n ) 5, 6, 7, 8,
10, 12, and 14, respectively.
Finally, sodium chloride was used as an electrolyte and
deionized water was used for the preparation of all the
aqueous solutions.
Cloud Point Extraction Procedure. The cloud points (i.e.,
the temperature at which a given micellar solution splits
into two liquid phases in a reversible manner), denoted CP,
were determined in a classical way by heating the micellar
solutions above their CP and then by leaving their temperature to slowly decrease under intensive mixing, until the
instant of complete disappearance of the turbidity (the
temperatures at which the solutions became transparent were
assumed to be the cloud points). The determination was
repeated at least three times for each solution and the error
on the average values of CP did not exceed 1 C. For each
2342

OMD-14

0.2
0.3
1.0
2.8
5.9
9.5
12.4
14.7
15.2
13.1
9.8
6.4
3.8
0.4
0.2
0.1
2

0.1
0.1
0.3
0.4
1.3
1.7
2.5
5.1
10.2
16.2
19.5
19.5
13.4
6.1
0.5
1

4.9
1.5
6.3
12.6
18.5
19.7
15.8
10.1
5.4
2.4
1.0
0.4
0.1
0.06

denoted hereafter as OMD-n, where n refers to the average

degree of oxyethylation. The surfactants effectively tested
exhibited average degrees of oxyethylation ranging between
5 and 14 and their compositions determined by GC and HPLC
were reported in previous papers (23, 24). As an example, the
compositions of OMD-5, OMD-10, and OMD-14 are given in
Table 1. Such compositions are typical of narrow-range
ethoxylates with a maximal content of the corresponding
homologue [i.e., C11H23CO(OCH2CH2)5OCH3 in OMD-5,
C11H23CO(OCH2CH2)6OCH3 in OMD-6, etc.]. The products
also contain small amounts of unreacted methyl dodecanoate
(typically 5 wt % in OMD-5, 2 wt % in OMD-6 and only 0.4
wt % in OMD-8) and a few percent of both monomethyl
ethers of polyoxyethylene glycols and didodecanoates of
polyoxyethylene glycols. Because of the complex composition
of the surfactants used, their concentrations are expressed
below in grams per liter (gL-1). However, using the following
equation allows a rough conversion into molarity:

COMD-n(M) knCOMD-n (gL-1)

OMD-10

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 35, NO. 11, 2001

OMD-n (n ) 5-14), the concentration of surfactant and that

of sodium chloride were changed between 0 and 50 gL-1
and 0 and 4 M, respectively.
The separation experiments were performed with aqueous
solutions containing 25 gL-1 of OMD-n and initial concentrations of phenol, 4-methylphenol, or 4-nitrophenol ranging
between about 4 10-4 and 2.5 10-3 M. The concentration
of sodium chloride was equal either to 0 or 1 M and the pH
of the aqueous solutions was below 5.5 in all cases (at such
an acidity, phenol [pKa ) 9.9], 4-methylphenol [pKa ) 10]
and 4-nitrophenol [pKa ) 7] exist only under their molecular
forms). In practice, 5 mL of phenol, 4-methylphenol or
4-nitrophenol solution in pure water or in 2 M NaCl and 5
mL of 50 gL-1 surfactant solution were introduced into test
tubes, mixed by hand shaking, heated to 85 C, or any other
stated temperature, and maintained at this temperature for
15 or 8 h in the absence or presence of (1 M) NaCl,
respectively. The surfactant-rich phase and the aqueous
solution were then cautiously separated. The extraction data
are expressed hereafter in terms of distribution coefficient
(D ) CS/CW, where CS and CW expressed in molarity denote
the solute concentration in the surfactant-rich phase and in
the aqueous solution, respectively) and/or percentage of
extraction (E[%] ) percent of solute in the surfactant-rich
phase). In fact, CW ) CW,dissolv + Cmicelles where CW,dissolv refers
to the concentration of solute actually dissolved in water
and Cmicelles represents the concentration of solute incorporated in the micelles remaining in aqueous phase after settling
of the surfactant-rich phase. In the present work, only CW
was determined experimentally as reported below.
Analytical Procedure. The concentrations of phenol,
4-methylphenol, and 4-nitrophenol in aqueous solutions (CW)
were determined spectrophotometrically at 270 nm (max )
1.4 103 mol-1Lcm-1), 278 nm (max ) 1.6 103
mol-1Lcm-1), and 317 nm (max ) 1.0 104 mol-1Lcm-1),
respectively, by using a SECOMAM S.750 spectrophotometer
(France). The molar absorption coefficient values found are
in agreement with those reported in the literature (25).
The efficiency of phase separation was estimated from
the measure of OMD-n concentrations in the aqueous
solutions by interferometry with a CARL ZEISS LI 3 type
interferometer (Germany), before and after demixtion (26).

TABLE 2. Cloud Points (C) of Aqueous Solutions Containing

10 gL-1 of Oxyethylated Methyl Dodecanoates (OMD-n) or
Oxyethylated Alcohols (C12/14)
avg degree of
oxyethylation

C11H23CO(OCH2CH2)nOCH3
(OMD-n)

C12/14H25/29(OCH2CH2)nOH
(27)

n)7
n)9
n ) 11
n ) 12
n ) 13

24
50
62
68
72

37
67
86
93
96

FIGURE 1. Cloud point of aqueous solutions containing various

oxyethylated methyl dodecanoates (OMD-n, with n ) 5-14).

Results and Discussion

Cloud Point. The effects of the hydrophilicity and concentration of the oxyethylated methyl dodecanoates on the cloud
point are exemplified in Figure 1. This figure shows that the
hydrophilicity measured in the scale of average degree of
oxyethylation n has a great influence on the cloud point,
whereas the OMD-n concentration has almost not effect,
except at the lowest concentrations. Above 10 gL-1, the cloud
point increases from a few C up to about 75 C according
to eq (3) when n is increased from 5 to 14 (in the absence
of electrolyte):

CP(C) ) -0.6742n2 + 20.92n - 86.81, r ) 0.995 (3)

The effect of hydrophilicity of the surfactants on the cloud
point can be discussed further by considering the hydrophilelipophile balance scale defined by Griffin (HLBG) (2). In this
scale, HLBG values vary between 0 and 20 for nonionic
surfactants. Products showing HLBG values lower than 10
exhibit a hydrophobic character, while those with HLBG values
above 10 are hydrophilic in nature. For nonionic surfactants
with a polyoxyethylene group, but containing neither nitrogen
nor sulfur atoms and no polyoxypropylene groups, the HLBG
values can be estimated by using eq 4 (2):

HLBG ) 20MH/MS

(4)

where MH and MS denote the molecular weight of the

hydrophilic groups and the molecular weight of the surfactant, respectively. For the OMD-n surfactants, a series of
HLBG values can be calculated with eq 4 by considering in
each case the corresponding homologue [i.e., C11H23CO(OCH2CH2)5OCH3 in OMD-5, C11H23CO(OCH2CH2)6OCH3 in
OMD-6, etc.]. The obtained values of HLBG range between
12.2 (n ) 5) and 15.9 (n ) 14). A point of interest is that a
straight line can simulate the plot of CP vs HLBG:

CP(C) ) 20.27 HLBG - 245.8 for [OMD-n] >

10 gL-1, r ) 0.994 (5)
which reflects a direct relationship between CP and the
hydrophilicity of OMD-n.
Table 2 shows that the studied OMD-n give lower cloud
points than the corresponding oxyethylated alcohols (i.e.,
having the same degree of oxyethylation), which suggests
that the OMD-n are less hydrophilic than the latter.
In practice, the oxyethylated methyl dodecanoates with
low average degrees of oxyethylation (i.e., n ) 5 or 6) are not
suitable for separations because their aqueous solutions are

FIGURE 2. Effect of sodium chloride on the cloud point of aqueous

solutions containing 10 gL-1 of various oxyethylated methyl
dodecanoates (OMD-n, with n ) 6-14).
already turbid at room temperature. Similarly, OMD-n with
n above 10 are not optimal for separations because the cloud
point occurs above 60 C, which is a drawback as a large
quantity of energy is then needed to heat the micellar
solutions and obtain the phase splitting. The reality is still
worse as an overheating (T ) Tset - CP, where Tset refers
to the settling temperature) of more than 10 C is essential
to obtain a surfactant-rich phase less hydrophilic (i.e., with
a low content of water) and, as a result, higher distribution
coefficients of phenols (see below). Thus, the use of oxyethylated methyl dodecanoates with average degrees of
oxyethylation ranging between 8 and 10 should be preferred.
Figure 2 shows that the cloud point decreases almost
linearly with NaCl concentration and approximately with
the same slopes for all the OMD-n [CP/[NaCl] -(9 (
1) CM-1]. This is due to a salting-out effect.
Efficiency and Characteristics of the Phase Separation.
Preliminary experiments carried out in the absence of phenols
showed that 15 and 8 h are needed to obtain the separation
of the surfactant-rich phase from the aqueous solution in
the absence and presence of (1 M) sodium chloride,
respectively. Such a difference is related to the density of the
surfactant-rich phase and that of the aqueous solution. In
the absence of electrolyte, the densities of the two phases
are close. In fact, the surfactant-rich phase containing OMD-7
has a density slightly lower than that of the aqueous solution
and separates as the top phase. More hydrophilic surfactants,
i.e., with n ) 9, 11, 12, and 14, have higher densities and
separate as the bottom phase. In the presence of 1 M NaCl,
the surfactant-rich phase always separates as the top phase
and, chiefly, more quickly. Thus, the addition of sodium
chloride not only decreases the cloud point but also
accelerates the coalescence of the fine droplets of the
surfactant-rich phase.
The volume of the surfactant-rich phase and, as a result,
the volume phase ratio (VS/VW) sharply decrease with
VOL. 35, NO. 11, 2001 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

2343

FIGURE 3. Influence of overheating (T ) Tset - CP) on the volume

phase ratio (VS/VW) for OMD-9 and OMD-11 initially at 25 gL-1 in
water. VS and VW denote the volumes of the surfactant-rich and
aqueous phases, respectively.

FIGURE 4. Distribution isotherms of phenol (Ph), 4-methylphenol

(Me-Ph) and 4-nitrophenol (NO2-Ph) between the aqueous and OMD9-rich phases, at 70 C (i.e., T ) 20 C) (the concentrations are
expressed in millimolar).

overheating (T ) Tset - CP) as exemplified in Figure 3, for

OMD-9 and OMD-11. Such a phenomenon has already been
reported by Akita et al. (16) and is due to a decrease of the
water content in the surfactant-rich phase. Beyond about
T ) 15 C, the ratio VS/VW reaches almost constant values.
Interferometric determinations (26) showed that about 85%
of OMD-n initially present at 25 gL-1 in pure water separates
as the surfactant-rich phase. This means that about 15% of
OMD-n remains in water, i.e., at concentrations close to
5 10-3 M, which is about 2 orders of magnitude higher
than the corresponding critical micelle concentrations
[CMC 5 10-5 M in pure water for OMD-n with n ) 7-14
(23)]. Interestingly, about 99% of OMD-n separates as the
surfactant-rich phase in the presence of 1 M NaCl, which
leads to residual OMD-n concentrations in the aqueous phase
close to 5 10-4 M. This is due, at least in part, to a more
rapid coalescence of the fine droplets of the surfactant-rich

phase and suggests that the losses of surfactant could be

significantly reduced compared to the preceding figures,
especially in the absence of electrolyte, by appropriate
chemical engineering treatment (e.g., centrifugation).
From mass balance, it can be calculated that the OMD-9
and OMD-11 surfactant-rich phases contain about 15 M water
in the valley region (i.e., T > 15 C), which is in a good
agreement with the direct water determinations currently
being made by the Karl-Fisher method. It can also be
calculated that the molar ratio water/OMD-n oxygen atom
in the surfactant-rich phase is close to 1 in this region, which
indicates that each oxygen atom of the OMD-n molecules
(present in carboxylate or oxyethylene groups) is still solvated
by one molecule of water in average.
Cloud Point Extraction of Various Phenols. The extraction data are summarized in Tables 3 and 4 and in Figure 4.
The efficiency of the extraction increases in the following

TABLE 3. Influence of Overheating (T ) Tset - CP) on the Distribution Coefficients and Percentages (E[%]) of Extraction of
Various Phenols, with OMD-9 as Surfactanta
settling temp,
Tset (C)

overheating
T (C)

phase ratio
(VS/VW)

60

10

5.3 10-2

70

20

3.0 10-2

80

30

3.0 10-2

phenol

4-methylphenol

4-nitrophenol

log10 D ) 1.31
E[%] ) 51.3
log10 D ) 1.62
E[%] ) 55.8
log10 D ) 1.54
E[%] ) 50.6

log10 D ) 1.55
E[%] ) 64.7
log10 D ) 1.80
E[%] ) 65.5
log10 D ) 1.72
E[%] ) 61.0

log10 D ) 1.75
E[%] ) 74.6
log10 D ) 1.99
E[%] ) 75.0
log10 D ) 1.90
E[%] ) 70.4

a Initial OMD-9 concentration ) 25 gL-1 (about 4 10-2 M); initial solute concentration ) 0.1 gL-1 in water (i.e., 1.06 10-3 M phenol; 9.2
10-4 M 4-methylphenol and 7.2 10-4 M 4-nitrophenol).

TABLE 4. Distribution Coefficients (in logarithmic scale) and Percentages (E[%]) of Extraction of Various Phenols (initially 0.1
gL-1) in the Absence or Presence of NaCl, at 85 C
surfactant
(25 gL-1)
OMD-9

NaCl
(M)
0

phase ratio
3.03

10-1

35

10-1

17
12

OMD-12

3.09

OMD-14

3.95 10-1

OMD-9
OMD-12
OMD-14

1
1
1

2344

overheating
T (C)

nd
nd
nd

48
32
28

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 35, NO. 11, 2001

phenol

4-methylphenol

4-nitrophenol

log10 D ) 1.50
E[%] ) 48.8
log10 D ) 1.58
E[%] ) 53.9
log10 D ) 1.35
E[%] ) 46.9
E[%] ) 53.0
E[%] ) 58.1
E[%] ) 54.2

log10 D ) 1.77
E[%] ) 64.2
log10 D ) 1.82
E[%] ) 67.2
log10 D ) 1.72
E[%] ) 67.3
E[%] ) 69.0
E[%] ) 72.6
E[%] ) 71.4

log10 D ) 1.88
E[%] ) 69.9
log10 D ) 1.84
E[%] ) 68.3
log10 D ) 1.76
E[%] ) 69.4
E[%] ) 78.5
E[%] ) 78.4
E[%] ) 82.0

TABLE 5. Experimental and Predicted Distribution Coefficients (log10 D), Binding Constants (log10 K), and Extraction Constants
(log10 KCP) of Various Phenols in Different Two-Phase or Pseudo Two-Phase Systems

solute
phenol
4-methylphenol
4-nitrophenol

cloud point extraction cloud point extraction

cloud point extraction
micellar extraction
cloud point extraction
with OMD-9 (log10 D)a with PONPE 10 (log10 D)a with PONPE 10 (log10 D)a with Brij-35 (log10 K)b with OMD-9 (log10 KCP)c
(from Figure 4)
(from eq 7)
(from eq 8)
(from eq 9)
(from Figure 4)
1.47
1.76
2.00

0.87
1.50
2.20

0.90
1.44
1.80

2.24
2.70
3.51

1.66
2.22
3.12

a D ) C /C . b K ) C
c
S W
micelles/[CW,dissolv (Csurf - CMC)]. KCP ) CS/[CW,dissolvCOMD-9/S]; where CS, CW, Cmicelles, CW,dissolv, Csurf, CMC and COMD-9/S are
expressed in molarity, and K and KCP are expressed in (molarity)-1. CS and CW denote the concentration of solute in the surfactant-rich phase and
in the aqueous solution, respectively. Cmicelles refers to the solute concentration in the pseudomicellar phase, whereas CW,dissolv represents the
concentration of solute actually dissolved in water. Csurf and CMC stands for the total concentration of surfactant in the aqueous phase and the
critical micelle concentration, respectively. Finally, COMD-9/S denotes the concentration of OMD-9 in the surfactant-rich phase. In the calculation
of KCP, the values of CW,dissolv were calculated by subtracting from CW the amount of solute in the aqueous micelles estimated by using the micellar
extraction constants reported for Brij-35.

order: phenol < 4-methylphenol < 4-nitrophenol. However,

under certain conditions, there is only a small difference
between the extractability of 4-methylphenol and 4-nitrophenol (e.g., see Table 4). Table 3 shows that the distribution
coefficients first increase with overheating (T), then reach
a maximum and finally decrease at high values of T and/or
Tset. It also appears from Tables 3 and 4 that despite
distribution coefficient values ranging between about 20 and
100, the yields of extraction do not exceed about 70-80% in
a single stage, as a result of low phase ratio values. In a process,
this drawback could be overcome by designing a multistage
flowsheet. Furthermore, aqueous effluents often contain
significant amounts of electrolytes whose presence strengthens the extraction of phenols by salting-out effect as
exemplified in Table 4. Except for phenol, the distribution
isotherms plotted in Figure 4 reveals a direct proportionality
between CS and CW. This indicates that the distribution
coefficients of 4-methylphenol and 4-nitrophenol remain
constant and suggests that the loading of the surfactant-rich
phases is far from saturation in all the range of solute
concentrations investigated. The corresponding distribution
coefficient values are given in Table 5. For phenol itself, a
linear relationship is observed between CS and CW, but the
obtained straight line does not cross axes origin. This could
be due to a by-side extraction arising from the presence of
low concentrations of impurities in OMD-9. If the latter
phenomenon is ignored, the distribution coefficient of phenol
can also be assumed to be constant within the whole range
of solute concentrations investigated and taken equal to the
slope of the linear part of the plot. The corresponding value
obtained is given in Table 5.
To understand the physicochemical phenomena involved
in the cloud point extraction of phenols, the preceding results
can be discussed on the basis of the general linear solvation
energy relationship [LSER] (eq 6) introduced by Abraham
(28, 29):

log Pi ) c + aR2 + b2 + s2 + rR2 + v(Vx/100) (6)

In addition to a constant c dependent on the variable Pi of
interest and the choice of standard states, eq 6 contains five
solute-specific, medium-insensitive, parameters (R2, 2,
2, R2, and Vx) whose relative contributions are dictated by
five numerical coefficients (a, b, s, r, and v, respectively). The
five parameters account for physical properties as follows:
R2 is the solute hydrogen-bond acidity; 2 is the solute
hydrogen-bond basicity; 2 is the solute dipolarity/polarizability, R2 is the solute excess molar refraction; Vx is the
McGowan characteristic volume (Vx) which is a descriptor
of solute hydrophobicity. The values of Vx (in cm3/mol) can
be calculated from molecular structures (30), whereas the
values of the other four parameters are available in the
literature (28-34). Equation 6 has been used to discuss the

distribution of solutes between water and micelles in micellar

extraction systems (31, 34, 35) and between aqueous solutions
and surfactant-rich phases in cloud point extraction systems
(36). In such systems, the distribution coefficient of solute,
D, is often used as the variable Pi. Using this approach it was
recently demonstrated that R2, 2, and Vx are the most
important parameters influencing the distribution of solutes
between water and surfactant-rich phases when PONPE 10
[polyoxyethylene nonyl phenyl ether having average chain
length of 10 oxyethylene units] is used as surfactant (36). An
increase of R2 and Vx causes an increase of log D, whereas
an increase of 2 has the opposite effect. The effect of the
other parameters depends on the nature of the surfactant
and solute considered. Thus, the following linear solvation
energy relationship was initially proposed for a series of
solutes including phenol, but neither 4-methylphenol nor
4-nitrophenol (36):

log10 D ) -2.85 + 0.544R2 - 3.432 + 0.938R2 +

4.73(Vx/100) (7)
A correlation of better quality was obtained by omitting the
free term and the term related to R2 and introducing the
term (Vx)2 instead of Vx (36):

log10 D ) 0.321 R2 - 2.48 2 + 2.42(Vx/100)2 (8)

Similar positive effects of R2 and Vx and negative effect of
2 were previously found for the incorporation of nonionic
solutes (including phenol) in nonionic Brij-35 (polyoxyethylene dodecyl ether having average chain length of 23
oxyethylene units) micelles (35):

log10 K ) -1.39 + 1.62R2 - 3.832 - 0.372 +

1.63R2 + 3.65(Vx/100) (9)
where K stands for the binding constant [expressed in
(molarity)-1].
By using the values of the solute-specific parameters
published by Abraham et al. for phenol, 4-methylphenol (also
called p-cresol) and 4-nitrophenol (31) and eqs 7-9, the
predicted values of log10 D and log10 K given in Table 5 were
calculated. Such predicted values of log10 D range in the same
order of magnitude as the experimental values of log10 D
obtained in the present system and increase according to
the same sequence: phenol < 4-methylphenol < 4-nitrophenol. Furthermore, by considering the micellar extraction
phenomena which takes place in the aqueous phase and
competes with the extraction of solute into the surfactantrich phase, one can calculate a more fundamental extraction
constant (KCP) which can be compared directly with the
binding constant K. Examination of Table 5 shows that log10
KCP and log10 K exhibit close values. All these observations
VOL. 35, NO. 11, 2001 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

2345

suggest that the extraction of the three considered phenols

in PONPE 10-rich phase and in OMD-n-rich phase and their
binding on Brij-35 micelles are based on similar phenomena.
As a result, eqs 7-9 can be tentatively used to better
understand the physico-chemistry of the distribution of
phenol, 4-methylphenol, and 4-nitrophenol between the
OMD-n-rich phases and aqueous solutions. For instance, eq
8 which contains only three parameters suggests that
4-methylphenol is extracted into OMD-n-rich phases more
efficiently than phenol because the contribution of the
hydrophobic effect to log10 D increases much more [i.e.,
2.42(Vx/100)2 ) +0.577] than the contribution arising from
the acidity effects decreases [i.e., 0.321R2 - 2.482 )
-0. 034], when 4-methylphenol replaces phenol. Similarly,
4-nitrophenol is extracted more efficiently than phenol and
4-methylphenol because both the contribution of hydrophobic effect and that of acidity effects increase when
4-nitrophenol replaces phenol or 4-methyphenol. Due to a
lack of appropriate data, some effects cannot be discussed
from the preceding equations. The influence of temperature
is a typical example. It can merely be pointed out that the
increase of log10 D with temperature at moderate values of
T (Table 3) may arise from the fact that the surfactant-rich
phase becomes less hydrophilic (i.e., more hydrophobic) and
exhibits more affinity for phenols as the settling temperature
Tset is increased. However, from the data reported in Figure
3, it could be expected that the hydrophobicity of the
surfactant-rich phase remains constant beyond a given
temperature and that the distribution coefficients of solutes
also reach constant values. This is not the case as a decrease
of the distribution coefficients is observed for the highest
values of T and/or Tset. A possible explanation is that the
solute transfer from the aqueous solution to the surfactantrich phase may be exothermic and that the resulting negative
effect may become prevalent at high temperature. The
influence of the average degree of oxyethylation of OMD-n
is also complex and certainly correlated with the temperature
effects.

Acknowledgments
The work was supported by the Poznan University of
Technology (Grant BW 32/326) and the French-Polish
POLONIUM program (Grants 98030 and 01818XD).

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Received for review February 4, 2000. Revised manuscript

received October 4, 2000. Accepted February 15, 2001.
ES000025Y