Journal of Colloid and Interface Science 298 (2006) 441–450

www.elsevier.com/locate/jcis

Calculation of hydrophile–lipophile balance for polyethoxylated surfactants

by group contribution method
Xiaowen Guo, Zongming Rong ∗ , Xugen Ying
Department of Chemistry, East China University of Science and Technology, Shanghai 200237, People’s Republic of China
Received 28 October 2005; accepted 5 December 2005
Available online 18 January 2006

Abstract
Based on Davies’ group contribution method, hydrophile–lipophile balance (HLB) values were calculated by effective chain length (ECL)
instead of actual chain length of straight alkyl chain, polyoxyethylene (EO) chain, and polyoxypropylene (PO) chain. Linear equations were
adopted for the effective chain length of straight alkyl chain and PO chain; a Gamma probability density function (PDF) was used to describe
the contribution of each EO group to HLB and the effective chain length of EO chain could be obtained by integrating Gamma PDF. The HLB
values of 224 nonionic surfactants were calculated and the average absolute error is less than 1.5, which is much better than the results obtained
by Davies.
© 2005 Elsevier Inc. All rights reserved.

Keywords: HLB; Group contribution method; Polyethoxylated surfactants; Effective chain length; Gamma PDF

1. Introduction Though Davies’ method is easy, except for several surfac-

The hydrophile–lipophile balance (HLB) of a surfactant, one
of the most widely used indicators of its suitability for a given
application is a measure of a surfactant partitioning tendency
between oil and water. Since Griffin first introduced this de-
finition in 1949 [1], there have been large numbers of works
to relate HLB value with various characters of surfactants in
order to develop a rapid and reproducible technique to deter-
mine HLB value experimentally or computationally [2–6]. Yet,
among all those methods, Davies’ method has been most widely
used [3,7]. He assumed that the HLB value was an additive and
constitutive indicator and the group numbers were assigned to
various structural elements. Then the HLB value was given by
 factant to the interface. However, Lin’s work has not improved
HLB = 7 + (hydrophilic group numbers)

+ (lipophilic group numbers).
* Corresponding author.
E-mail address: rongzm@sh163c.sta.net.cn (Z. Rong).
0021-9797/$ – see front matter © 2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.12.009
tants, some HLB values obtained by this method are erroneous,
and some surfactants cannot be calculated because of a lack of
group numbers. For surfactants with a polyoxyethylene (EO)
chain as the sole hydrophilic moiety, Davies’ HLB values differ
greatly from experimental data. In some extreme cases, Davies’
HLB values are negative, which is apparently unreasonable;
hence the Davies method is unsuitable for most nonionic sur-
factants [8,9]. Lin et al. [10–13] introduced the concept of ef-
fective chain length to modify the Davies equation and obtain
empirical expressions for effective chain length based on the
critical micelle concentration. Lin’s work improved the con-
sistency between calculated results and experiments, especially
for polyethoxylated ionic surfactants. He related Davies’ em-
pirical group numbers to the free energy of transfer of the sur-
the calculation errors of polyethoxylated nonionic surfactants’
(1) HLB; thus it only mitigates the objections to the Davies ap-
proach. McGowan and co-workers [14,15] calculated group
numbers on the basis of known atomic volume Vx . They ob-
tained about 30 lipophilic group numbers and 30 hydrophilic
group numbers, which were nearly the same as those of Davies
442 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450

and Lin, except for anionic group numbers. But they also did
not improve the calculation errors of polyethoxylated nonionic
surfactants’ HLB values.
In this paper, partly based on Davies’ method, the calcula-
tion errors of HLB values for polyethoxylated surfactants were
improved by the introduction of effective chain length (ECL)
for straight alkyl chain, EO chain, and polyoxypropylene (PO)
chain.

2. Equations of the effective chain length

In the Davies method, for a surfactant that contains –CH2 –,

EO, PO, and other groups, Eq. (1) can be written as
Fig. 1. Plot of NEO,eff values against NEO values for ethoxylated alcohols, etho-
xylated fatty acid esters, and ethoxylated alkyl phenols.
HLB = 7 + GNCH2 × NCH2 + GNEO × NEO + GNPO × NPO

+ (other hydrophilic groups)

+ (other lipophilic groups), (2)
where GNCH2 , GNEO , and GNPO are group numbers for
–CH2 –, EO, and PO. NCH2 , NEO , and NPO represent the ac-
tual chain lengths for –CH2 –, EO, and PO groups. “Other
hydrophilic groups” refers to hydrophilic groups except EO
and “other lipophilic groups” refers to lipophilic groups except
–CH2 – and PO.
In this work, HLB should be given by

HLB = 7 + GNCH2 × NCH2 ,eff + GNEO × NEO,eff

+ GNPO × NPO,eff

+ (other hydrophilic groups)

+ (other lipophilic groups),
where NCH2 ,eff , NEO,eff , and NPO,eff represent the effective
chain length for –CH2 –, EO, and PO groups; i.e., the actual
chain length is replaced by the effective chain length during the
calculation. The parameters of the effective chain length are re-
lated to group numbers. Since group numbers for –CH2 –, EO,
and PO are known, in this work, they are assumed to be −0.475,
0.33, and −0.15 just the same as those of Davies.
As for a straight alkyl chain, the fully stretched lipophilic
chain length is directly proportional to the number of –CH2 –
groups [16,17]; therefore, it is reasonable to use the effective
chain length to describe their contribution to HLB value. Ac-
cording to the relation between the HLB published data and the
number of –CH2 – groups, NCH2 ,eff is given by
NCH2 ,eff = 0.965NCH2 − 0.178.
When Eq. (4) and the published HLB values of polyethoxy-
lated surfactants are substituted into Eq. (3), subtracting the
contribution of other groups to the HLB value, the effective
chain length of EO can be calculated. Fig. 1 shows the com-
parison of actual EO chain length and effective chain length
of polyethoxylated alcohols, polyethoxylated fatty acid esters,
and polyethoxylated alkyl phenols. In Fig. 1, the dashed line
is made up of smooth data, with the main trend being elicited
from the scattered data.
Fig. 2. The two-parameter Gamma PDF and its integral curve.
(3)
If the Gamma probability density function (PDF) is used to
calculate the contribution of each EO group to the HLB value,
then the contribution of the whole EO chain to HLB can be
calculated by the integral of the Gamma PDF. The relationship
between the effective chain length of the EO chain and the ac-
tual chain length is thereby written as

NEO
NEO,eff = A f (N ) dN, (5)
0
α β−1
where f (N) = β ΓN(α) e−βN is the Gamma PDF and A is the
normalization coefficient. Equation (5) was fitted to the smooth
data using optimization. It was obtained that α = 0.4406, β =
0.0245, and the normalization coefficient A = 52.57. NEO,eff
(4)
calculated by Eq. (5) is shown by the solid line in Fig. 1.
Although Gamma PDF may give a good explanation of the
contribution of the EO chain to HLB, it is inconvenient to cal-
culate; thus its application is confined. To make the calculation
of the effective chain length of EO chain easy, an empirical
subsection function was put forward, which is also fitted to
the smooth data. As shown in Eq. (5 ), NEO = 50 is supposed
to be the division point in the subsection function, because
the number of EO groups in most nonionic surfactants is less
than 50. Besides, when NEO reaches 50, the contribution of
 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450 443

Table 1
The group numbers obtained by the Davies and Lin and ECL method
Hydrophilic group numbers Lipophilic group numbers
Group Davies and Lin ECL method Group Davies and Lin ECL method
–SO4 Na 38.7 38.4 –CH– −0.475 −0.475
–COOK 21.1 20.8 –CH2 – −0.475 −0.475
–COONa 19.1 18.8 –CH3 −0.475 −0.475
–SO3 Na 11 10.7 =CH– −0.475 −0.475
–N (tertiary amine) 9.4 2.4 –CF2 – −0.87 –
Ester (free) 2.4 2.316 –CF3 −0.87 –
–COOH 2.1 1.852 Phenyl −1.662 −1.601
–OH (free) 1.9 2.255 –CH2 CH2 CH2 O– −0.15 −0.15
–CH2 OH – 0.724 –CH(CH3 )CH2 O– −0.15 −0.15
–CH2 CH2 OH – 0.479 –CH2 CH(CH3 )O– −0.15 −0.15
–CH2 CH2 CH2 OH – 0.382 Sorbitan ring – −20.565
–O– 1.3 –
–CH2 CH2 O– 0.33 0.33
–CH2 CH2 OOC– – 3.557
–OH (sorbitan ring) 0.5 5.148
Ester (sorbitan ring) 6.8 11.062

EO chain to the HLB value has taken up about 90% (given by
Fig. 2):
 Substituting the above-mentioned effective chain length
13.45 ln(NEO ) − 0.16NEO + 1.26, 1  NEO  50,
NEO,eff =
0.056NEO + 43.08, NEO  50.
(5 )
In addition, poly(ethylene oxide)–poly(propylene oxide)
(PEO–PPO) block copolymers are also one kind of common
surfactants. As a lipophilic group, the effective PO chain length
is given by the linear equation
NPO,eff = 2.057NPO + 9.06,
where NPO,eff and NPO represent the effective PO chain length
and actual PO chain length, respectively.
When the effective chain length for straight alkyl chains, EO
chains, and PO chains is used, other group numbers should be
adjusted accordingly. The calculated HLB values were fitted
with the published data to obtain the group numbers for groups
other than –CH2 –, EO, and PO. A set of group numbers were
obtained and they are shown in Table 1, together with those of
Davies and Lin.
In Table 1, several new groups are introduced. The reasons
for introducing –CH2 OH, –CH2 CH2 OH, –CH2 CH2 CH2 OH,
–CH2 CH2 OOC–, and sorbitan ring groups are as follows. Take
PEO(4) monolaurate for example, we treat –CH2 CH2 OH at the
end of CH3 (CH2 )10 COOCH2 CH2 OCH2 CH2 OCH2 CH2 OCH2 –
CH2 OH as a whole group. This is because at the O/W interface
the –CH2 – groups in close proximity are influenced by the
apparent atmosphere of strong hydrophilic hydroxyl. Their con-
tribution to HLB is changed and cannot be simply added like
Davies did. Besides, we treat the sorbitan ring as a whole, be-
cause when –CH2 – and –O– groups form a ring, the structure
has a certain steric effect and groups will be influenced by each
other. Thus their contribution to HLB is not the same as when
they are in a straight alkyl chain.
3. Results and discussion
equations and group numbers into Eq. (3), HLB values of 224
nonionic surfactants were calculated and compared with the re-
sults obtained by the Davies method. These results are all listed
in Appendix B. Additionally, the results calculated by both
Eqs. (5) and (5 ) are listed when the ECL method was used;
they are almost the same. Table 2 lists the average absolute er-
rors and the maximum errors of the HLB values of different
types of surfactants calculated by the ECL method and Davies
method. It is clear that the results obtained by the ECL method
(6) are much better than those obtained by the Davies method, ex-
cept for polyhydric alcohol esters without EO groups, Span,
and Tween surfactants, whose calculation results are almost the
same as those obtained by Davies. Therefore, using Eqs. (5)
and (5 ) to calculate the effective EO chain length is reason-
able.
Since HLB is a measure of the partitioning tendency of the
surfactants between oil and water, its value is proportional to
the surfactants’ solubility in water. Polyethoxylated surfactants
are able to dissolve in water because of their hydration; in water
solution, water molecules are directly bound to the hydrophilic
site, i.e., the oxygen atom in an ethylene oxide group, with four
water molecules per site. So there must be a lot of such oxygen
atoms to increase the solubility of lipophilic groups. Consider-
ing the steric effects, only when the EO chain has a configura-
tion of a zigzag is it possible for an oxygen atom to associate
with as many as four water molecules. In 1956, according to
experimental X-ray results, Rösch concluded that only the first
10–12 EO groups in the EO chain form a zigzag, while the
rest form a right angle [18]. And according to the measured
viscosity, Heusch also suggested that each EO group may asso-
ciate with a maximum of six water molecules within a certain
temperature [19]. Therefore, when EO groups in surfactants
increase, they do not make the same hydrophilic contribution
to HLB. Davies did not take this fact into account, while the
444 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450

Table 2
Errors of the HLB values calculated by the Davies method and the ECL method
Types of surfactants Numbers Davies method ECL method
Eq. (5) Eq. (5 )
¯a
 max ¯
 max ¯
 max
Ethoxylated alcohols 51 6.61 9.25 1.09 3.89 0.78 3.57
Ethoxylated fatty acid esters 38 7.57 32.65 0.84 2.71 0.73 2.38
Ethoxylated dialkyl acids 17 11.04 30.87 1.86 3.63 1.89 3.75
Ethoxylated alkylphenols 34 6.34 29.19 0.9 3.62 0.67 2.42
Polyhydric alcohol ester 14 2.79 9.23 1.94 7.50 1.94 7.50
Amine 8 2.74 7.79 0.68 3.14 0.97 6.42
Pluronic F/L/P block copolymers 31 10.69 62.57 3.64 6.62 3.66 7.23
Pluronic R block copolymers 16 11.93 65.87 1.44 4.17 1.44 4.64
Span and Tween 15 1.01 2.63 0.55 1.52 0.67 1.85
Total 224 7.26 65.87 1.46 7.50 1.36 7.50

¯ = 1 N |HLBc − HLB|, where HLBc is the HLB value calculated and HLB is the published data.
a 
N i=1

Gamma PDF describes this hydrophilic contribution much bet-
ter. In Fig. 2, the dotted line is the Gamma PDF, which describes
the contribution of each EO group to HLB. The solid line is
the integral of the Gamma PDF, which describes the increas-
ing trend of HLB. From Fig. 2, it can be seen that when EO
groups increase, their contribution to HLB decreases quickly.
Take a surfactant molecule containing 200 EO groups for ex-
ample. The effective chain length for its first three EO groups is
18; i.e., each oxygen atom in one EO group is able to associate
with six water molecules averagely. Therefore it can be con-
cluded that this part of the EO chain forms a zigzag and each EO
group has reached its maximum hydration ability. And the con-
tribution of these EO groups to HLB has taken up about 34%.
If extending to the first 10 EO groups, the effective chain length
is about 30; i.e., each EO group can associate with three water
molecules averagely, when EO groups still form a zigzag. And
the contribution of these 10 EO groups to HLB is about 56%.
If the EO groups increase to 50, the contribution of these EO
groups to HLB is close to 90%. The average number of water
molecules that are bound to each EO group will decline, which
shows that the configuration of the incremental EO groups has
changed. It is possible that the effective EO chain length is re-
lated to the number of water molecules that the surfactant is
bound to.
The errors obtained by the ECL method for Pluronic F/L/P
block copolymers were bigger than those of Pluronic R sur-
factants. This is because the component sequence (i.e., PEO–
PPO–PEO) of Pluronic F/L/P block copolymers is different
from Pluronic R surfactants. The chain length of EO groups
in two sides of copolymers was assumed to be equal in cal-
culation. Actually, it is difficult to get these products with
equal distribution of EO at two sides in the manufacturing.
Because the contribution of EO to HLB is nonlinear, there
are obvious differences when EO groups distribute differently
at two sides. As for Pluronic R surfactants, which are tri-
block copolymers with the sequence PPO–PEO–PPO, since the
equation for the effective PO chain length is linear, no matter
how PO groups distribute at two ends of the polymer, the re-
sults are only related to the total number of PO numbers. The
comparatively small errors of Pluronic R surfactants demon-
strated the proposed linear effective PO chain length equa-
tion.
Likewise, among Tween surfactants, the ethoxylated sorbi-
tan mono-fatty-acid esters whose EO chains may distribute at
three branches, the calculation results will be influenced a lot. In
this work, it was assumed for simplicity that EO groups were all
distributed at the single branch during the calculation. Though
the calculation results are in good agreement with experiments,
the group numbers for sorbitan ring, –OH and ester groups on
the sorbitan ring obtained in this way differed a lot from those
of Davies, they are only empirical numbers.
Concerning the four anionic groups in Table 1, i.e., –SO4 Na,
–COOK, –COONa, and –SO3 Na, a lot of researchers doubted
their group numbers [14,20–22]. However, as a result of lack-
ing experimental data, no standard has been established and
Davies’ HLB values about ionic surfactants have been still
adopted until now. Since the effective chain length equations
are used in calculation, these four ionic group numbers are ad-
justed accordingly to keep the HLB value unchanged.
4. Conclusions
In the present paper, emphasis was on the calculation of
HLB for polyethoxylated surfactants. Conclusions in details are
as follows. First, based on the Davies method, three effective-
chain-length equations for straight alkyl chain, EO chain, and
PO chain have been introduced. The effective chain length of
a surfactant molecule is of greater practical relevance than the
actual chain length; it represents the degree of hydrophobicity
or hydrophilicity of groups and is highly sensitive to the nature
of the structural modification. Second, the Gamma PDF was
used to describe the contribution of EO groups to HLB. This
is because when the number of EO groups increases, their con-
tribution to HLB decrease rapidly and the HLB value tends to
be a constant. Thus the integral of the Gamma PDF was used
to calculate the effective EO chain length. Since the calculation
of the Gamma PDF is a little complicated, an empirical sub-
section function can also be used to calculate the effective EO
chain length.
 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450 445

In this work, 224 nonionic surfactants were calculated. The absolute error is  = |HLBc − HLB| = |13.72 − 13.4| =
Through comparison with Davies method, HLB values cal- 0.32.
culated by ECL method are more reasonable and the average
(b) Pluronic F127 block copolymers:
errors are reduced greatly.
CH3
Acknowledgments |
HO(CH2 CH2 O) —(CHCH2 O) — (CH2 CH2 O) — H
a 65.2 b
The authors gratefully acknowledge the suggestions pro- (a = b = 100.2)
vided by the reviewers.
The effective PO chain length NPO,eff of this surfactant is
Appendix A. Examples of HLB calculation calculated by Eq. (6):

(a) POE(10) nonyl phenyl ether: NPO,eff = 2.057NPO + 9.06 = 2.057 × 65.2 + 9.06 = 143.18.
If Eq. (5) is used to calculate the effective EO chain length of
CH3 (CH2 )8 O–(CH2 CH2 O)10 –H.
this surfactant, NEO,eff (a) of the left EO chain, which contains
The effective straight alkyl chain length NCH2 ,eff of this sur- a EO groups, is
factant is calculated by Eq. (4):

NEO
β α Nβ−1 −βN
NCH2 ,eff = 0.965NCH2 − 0.178 = 0.965 × 9 − 0.178 = 8.507. NEO,eff (a) = A e dN
Γ (α)
Its effective EO chain length NEO,eff is calculated by Eq. (5): 0

100.2

NEO 0.1951 × N−0.9755 −0.0245N
β α Nβ−1 −βN = 52.57 e dN
NEO,eff = A e dN Γ (0.4406)
Γ (α) 0
0
= 50.99.
10
0.1951 × N−0.9755 The effective chain length of the EO chain on the right-hand
= 52.57 e−0.0245N dN = 29.27.
Γ (0.4406) side, which contains (b − 1) EO groups and one CH2 CH2 OH
0 (EOH) group, is
Then the HLB value is calculated according to Eq. (3):

NEO
β α Nβ−1 −βN
HLBc = 7 + GNCH2 × NCH2 ,eff + GNEO × NEO,eff NEO,eff (b) = A e dN
Γ (α)
+ GNPO × NPO,eff 0
 99.2
+ (other hydropilic groups) 0.1951 × N−0.9755 −0.0245N
= 52.57 e dN
 Γ (0.4406)
+ (other lipophic groups) 0
= 50.95.
= 7 + GNCH2 × NCH2 ,eff + GNEO × NEO,eff + GNOH
+ GNphenyl Then the HLB value calculated by Eq. (3):

= 7 − 0.475 × 8.507 + 0.33 × 29.27 + 2.255 − 1.601 HLBc = 7 + GNCH2 × NCH2 ,eff + GNEO × NEO,eff
= 13.27. + GNPO × NPO,eff

Since the published HLB value for this surfactant is 13.4, the + (other hydropilic groups)
absolute error is  = |HLBc − HLB| = 0.13. 
+ (other lipophic groups)
Alternatively, the effective EO chain length NEO,eff can also
be calculated by Eq. (5 ): = 7 + GNEO × NEO,eff (a) + GNEO × NEO,eff (b)
+ GNPO × NPO,eff + GNOH + GNEOH
NEO,eff = 13.45 ln(NEO ) − 0.16NEO + 1.26
= 7 + 0.33 × 50.99 + 0.33 × 50.95 − 0.15 × 143.18
= 13.45 ln(10) − 0.16 × 10 + 1.26 = 30.63.
+ 2.255 + 0.479 = 21.90.
Then the HLB value calculated by Eq. (3) is
Since the published HLB value is 22.0, the absolute error is
HLBc = 7 + GNCH2 × NCH2 ,eff + GNEO × NEO,eff + GNOH  = |HLBc − HLB| = 0.10.
+ GNphenyl If the effective EO chain length is calculated by Eq. (5 ), then
= 7 − 0.475 × 8.507 + 0.33 × 30.63 + 2.255 − 1.601 NEO,eff (a) = 0.056NEO + 43.08 = 0.056 × 100.2 + 43.08
= 13.72. = 48.69,
446 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450

NEO,eff (b) = 0.056NEO + 43.08 = 0.056 × 99.2 + 43.08 From the above two examples, the difference in calculated
= 48.64. results between Eqs. (5) and (5 ) is quite small. Both of them
can be used in the calculation of HLB value.
The HLB value calculated by Eq. (3):

HLBc = 7 + GNEO × NEO,eff (a) + GNEO × NEO,eff (b)
+ GNPO × NPO,eff + GNOH + GNEOH
= 7 + 0.33 × 48.69 + 0.33 × 48.64 − 0.15 × 143.18
+ 2.255 + 0.479 = 20.38.
The absolute error is  = |HLBc − HLB| = 1.62.
Appendix B. Calculation results of all surfactants
Tables 3–5 list all the calculation results for 224 nonionic
surfactants obtained both by the Davies method and by the ECL
method (Eqs. (5) and (5 ) are both used). The error of each sur-
factant is also included.

Table 3
The HLB values of ethoxylated alcohols, ethoxylated fatty acid esters, ethoxylated alkyl phenols, polyhydric alcohol esters, and amines calculated both by the
Davies method and the ECL method
Surfactant HLBa Davies method ECL method
HLBc  Eq. (5) Eq. (5 )
HLBc  HLBc 
Ethoxylated alcohols
POE(3) butyl ether 12.81 7.99 −4.82 13.43 0.62 12.64 −0.17
POE(4) pentyl ether 14.08 8.32 −5.76 14.20 0.12 13.86 −0.22
POE(3) pentyl ether 12.00 7.52 −4.49 12.97 0.97 12.18 0.18
POE(4) pentyl ether 13.33 7.85 −5.49 13.74 0.41 13.41 0.08
POE(5) octyl ether 13.50 6.75 −6.75 13.01 −0.49 12.97 −0.53
POE(1) lauryl ether 3.60 3.53 −0.07 7.49 3.89 4.17 0.57
POE(2) lauryl ether 9.50 3.86 −5.64 8.81 −0.69 7.23 −2.27
POE(3) lauryl ether 8.40 4.19 −4.21 9.76 1.36 8.97 0.57
POE(4) lauryl ether 10.10 4.52 −5.58 10.53 0.43 10.20 0.10
POE(5) lauryl ether 11.70 4.85 −6.85 11.18 −0.52 11.13 −0.57
POE(7) lauryl ether 12.10 5.51 −6.59 12.25 0.15 12.52 0.42
POE(8) lauryl ether 13.70 5.84 −7.86 12.71 −0.99 13.06 −0.64
POE(9) lauryl ether 13.30 6.17 −7.13 13.12 −0.18 13.53 0.23
POE(12) lauryl ether 14.80 7.16 −7.64 14.17 −0.63 14.65 −0.15
POE(15) lauryl ether 15.50 8.15 −7.35 15.02 −0.48 15.48 −0.02
POE(20) lauryl ether 15.00 9.80 −5.20 16.13 1.13 16.50 1.50
POE(23) lauryl ether 16.90 10.79 −6.11 16.67 −0.23 16.96 0.06
POE(3) tridecyl ether 8.00 3.72 −4.29 9.30 1.30 8.51 0.51
POE(6) tridecyl ether 11.20 4.71 −6.50 11.29 0.09 11.43 0.23
POE(9) tridecyl ether 13.10 5.70 −7.41 12.66 −0.44 13.07 −0.03
POE(10) tridecyl ether 13.80 6.03 −7.78 13.04 −0.76 13.49 −0.31
POE(11) tridecyl ether 14.10 6.36 −7.75 13.39 −0.71 13.86 −0.24
POE(12) tridecyl ether 14.60 6.69 −7.92 13.71 −0.89 14.19 −0.41
POE(15) tridecyl ether 15.40 7.68 −7.73 14.56 −0.84 15.02 −0.38
POE(3) tetradecyl ether 8.60 3.24 −5.36 8.84 0.24 8.06 −0.54
POE(7) tetradecyl ether 12.50 4.56 −7.94 11.33 −1.17 11.61 −0.89
POE(2) cetyl ether 5.70 1.96 −3.74 6.97 1.27 5.39 −0.31
POE(3) cetyl ether 8.00 2.29 −5.71 7.93 −0.07 7.14 −0.86
POE(6) cetyl ether 10.50 3.28 −7.22 9.91 −0.59 10.06 −0.44
POE(7) cetyl ether 11.80 3.61 −8.19 10.42 −1.38 10.69 −1.11
POE(8) cetyl ether 12.40 3.94 −8.46 10.87 −1.53 11.23 −1.17
POE(10) cetyl ether 12.90 4.60 −8.30 11.66 −1.24 12.11 −0.79
POE(15) cetyl ether 15.50 6.25 −9.25 13.19 −2.31 13.65 −1.85
POE(20) cetyl ether 15.30 7.90 −7.40 14.30 −1.00 14.66 −0.64
POE(25) cetyl ether 18.50 9.55 −8.95 15.15 −3.35 15.39 −3.11
POE(30) cetyl ether 19.50 11.20 −8.30 15.83 −3.67 15.93 −3.57
POE(2) stearyl ether 4.90 1.01 −3.89 6.06 1.16 4.48 −0.42
POE(3) stearyl ether 6.20 1.34 −4.86 7.01 0.81 6.22 0.02
POE(5) stearyl ether 8.90 2.00 −6.90 8.43 −0.47 8.38 −0.52
POE(7) stearyl ether 11.20 2.66 −8.54 9.50 −1.70 9.77 −1.43
POE(10) stearyl ether 12.40 3.65 −8.75 10.75 −1.65 11.2 −1.2
POE(15) stearyl ether 14.20 5.30 −8.90 12.27 −1.93 12.73 −1.47
POE(20) stearyl ether 15.30 6.95 −8.35 13.38 −1.92 13.75 −1.55
POE(21) stearyl ether 15.50 7.28 −8.22 13.57 −1.93 13.91 −1.59
(continued on next page)
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Table 3 (continued)
Surfactant HLBa Davies method ECL method
HLBc  Eq. (5) Eq. (5 )
HLBc  HLBc 
POE(40) stearyl ether 17.40 13.55 −3.85 15.90 −1.50 15.77 −1.63
POE(2) oleyl ether 4.50 1.01 −3.49 6.06 1.56 4.48 −0.02
POE(3) oleyl ether 6.60 1.34 −5.26 7.01 0.41 6.22 −0.38
POE(4) oleyl ether 8.00 1.67 −6.33 7.78 −0.22 7.45 −0.55
POE(5) oleyl ether 8.90 2.00 −6.90 8.43 −0.47 8.38 −0.52
POE(10) oleyl ether 12.40 3.65 −8.75 10.75 −1.65 11.20 −1.20
POE(20) oleyl ether 15.30 6.95 −8.35 13.38 −1.92 13.75 −1.55

Ethoxylated fatty acid esters

PEG(2) monolaurate 6.70 5.46 −1.25 8.49 1.79 5.17 −1.53
PEG(4) monolaurate 9.80 6.12 −3.69 10.76 0.96 9.97 0.17
PEG(6) monolaurate 10.95 6.78 −4.18 12.18 1.23 12.13 1.18
PEG(8) monolaurate 13.40 7.44 −5.97 13.25 −0.15 13.52 0.12
PEG(12) monolaurate 15.20 8.76 −6.45 14.85 −0.35 15.32 0.12
PEG(20) monolaurate 17.25 11.40 −5.86 16.93 −0.32 17.32 0.07
PEG(24) monolaurate 16.80 12.72 −4.09 17.66 0.86 17.96 1.16
PEG(40) monolaurate 17.90 18.00 0.10 19.56 1.66 19.45 1.55
PEG(100) monolaurate 19.10 37.80 18.70 21.65 2.55 20.92 1.82
PEG 6000 monolaurate 19.20 49.81 30.61 21.91 2.71 21.58 2.38
Ethylene glycol monostearate 2.20 2.28 0.07 2.09 −0.11 2.09 −0.11
PEG(2) monostearate 4.25 2.61 −1.65 5.74 1.49 2.42 −1.83
PEG(4) monostearate 7.20 3.27 −3.94 8.01 0.81 7.22 0.02
PEG(5) monostearate 8.55 3.60 −4.96 8.78 0.23 8.44 −0.11
PEG 300 monostearate 10.70 4.19 −6.51 9.96 −0.74 10.0 −0.70
PEG(8) monostearate 11.60 4.59 −7.02 10.50 −1.10 10.77 −0.83
PEG(9) monostearate 10.80 4.92 −5.89 10.95 0.15 11.31 0.51
PEG(10) monostearate 11.00 5.25 −5.76 11.37 0.37 11.78 0.78
PEG(11) monostearate 13.60 5.91 −7.70 12.10 −1.50 12.57 −1.03
PEG(15) monostearate 14.00 6.90 −7.11 13.00 −1.00 13.48 −0.52
PEG(20) monostearate 15.50 8.55 −6.96 14.18 −1.32 14.57 −0.93
PEG(24) monostearate 15.80 9.87 −5.94 14.91 −0.89 15.21 −0.59
PEG 1500 monostearate 17.00 13.20 −3.81 16.24 −0.76 16.29 −0.71
PEG(40) monostearate 17.20 15.15 −2.06 16.81 −0.39 16.70 −0.50
PEG(50) monostearate 17.90 18.45 0.55 17.51 −0.39 17.19 −0.71
PEG(75) monostearate 18.40 26.70 8.30 18.47 0.07 17.72 −0.68
PEG(100) monostearate 18.80 34.95 16.15 18.90 0.10 18.17 −0.63
PEG(150) monostearate 18.80 51.45 32.65 19.20 0.40 19.08 0.28
PEG(2) monooleate 4.10 3.11 −1.00 5.74 1.64 2.42 −1.68
PEG(4) monooleate 7.30 3.77 −3.54 8.01 0.71 7.22 −0.08
PEG(5) monooleate 8.30 4.10 −4.21 8.78 0.48 8.44 0.14
PEG(6) monooleate 9.70 4.43 −5.28 9.43 −0.27 9.38 −0.32
PEG 300 monooleate 8.90 4.69 −4.21 9.96 1.06 10.00 1.10
PEG (8) monooleate 11.50 5.09 −6.42 10.50 −1.00 10.77 −0.73
PEG (12) monooleate 13.15 6.41 −6.75 12.10 −1.05 12.57 −0.58
PEG (20) monooleate 15.40 9.05 −6.36 14.18 −1.22 14.57 −0.83
PEG 4000 monooleate 18.70 32.45 13.75 18.78 0.08 18.01 −0.69
PEG 6000 monooleate 19.00 47.46 28.46 19.16 0.16 18.83 −0.17

Ethoxylated dialkyl acids

PEG(4) dilaurate 6.65 1.39 −5.26 8.88 2.23 8.09 1.44
PEG(6) dilaurate 9.80 2.05 −7.75 10.30 0.50 10.25 0.45
PEG(8) dilaurate 10.25 2.71 −7.54 11.37 1.12 11.64 1.39
PEG(12) dilaurate 11.85 4.03 −7.82 12.97 1.12 13.44 1.59
PEG(20) dilaurate 14.50 6.67 −7.83 15.05 0.55 15.44 0.94
PEG(32) dilaurate 15.70 10.63 −5.07 16.89 1.19 16.98 1.28
PEG(75) dilaurate 17.60 24.82 7.22 19.34 1.74 18.59 0.99
PEG(150) dilaurate 18.70 49.57 30.87 20.07 1.37 19.95 1.25
Ethylene glycol distearate 1.55 −5.30 −6.85 1.34 −0.21 1.34 −0.21
PEG(4) distearate 4.95 −4.31 −9.26 3.38 −1.57 2.59 −2.36
PEG(8) distearate 8.00 −2.99 −10.99 5.87 −2.13 6.14 −1.86
PEG(12) distearate 10.30 −1.67 −11.97 7.47 −2.83 7.94 −2.36
PEG(32) distearate 14.80 4.93 −9.87 11.39 −3.41 11.48 −3.32
(continued on next page)
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Table 3 (continued)
Surfactant HLBa Davies method ECL method
HLBc  Eq. (5) Eq. (5 )
HLBc  HLBc 
PEG(150) distearate 18.20 43.87 25.67 14.57 −3.63 14.45 −3.75
PEG(4) dioleate 5.70 −4.31 −10.01 3.38 −2.32 2.30 −3.40
PEG(8) dioleate 8.50 −2.99 −11.49 5.87 −2.63 5.85 −2.65
PEG(12) dioleate 10.50 −1.67 −12.17 7.47 −3.03 7.65 −2.85

Ethoxylated alkylphenols
POE(1) octyl phenyl ether 4.10 3.77 −0.33 7.72 3.62 4.40 0.30
POE(3) octyl phenyl ether 7.30 4.43 −2.87 9.99 2.69 9.21 1.91
POE(4) octyl phenyl ether 9.65 4.76 −4.89 10.76 1.11 10.43 0.78
POE(5) octyl phenyl ether 10.20 5.09 −5.11 11.41 1.21 11.37 1.17
POE(6) octyl phenyl ether 11.20 5.42 −5.78 11.98 0.78 12.12 0.92
POE(7) octyl phenyl ether 12.00 5.75 −6.25 12.48 0.48 12.75 0.75
POE(8) octyl phenyl ether 12.60 6.08 −6.52 12.94 0.34 13.29 0.69
POE(9) octyl phenyl ether 13.30 6.41 −6.89 13.35 0.05 13.76 0.46
POE(10) octyl phenyl ether 13.60 6.74 −6.86 13.73 0.13 14.18 0.58
POE(11) octyl phenyl ether 14.00 7.07 −6.93 14.08 0.08 14.55 0.55
POE(12) octyl phenyl ether 14.60 7.40 −7.20 14.40 −0.20 14.88 0.28
POE(13) octyl phenyl ether 14.50 7.73 −6.77 14.70 0.20 15.19 0.69
POE(30) octyl phenyl ether 17.30 13.34 −3.96 17.89 0.59 18.00 0.70
POE(40) octyl phenyl ether 17.80 16.64 −1.16 18.88 1.08 18.75 0.95
POE(70) octyl phenyl ether 18.60 26.54 7.94 20.35 1.75 19.63 1.03
POE(1) nonyl phenyl ether 4.00 3.29 −0.71 7.26 3.26 3.94 −0.06
POE(2) nonyl phenyl ether 5.70 3.62 −2.08 8.58 2.88 7.00 1.30
POE(4) nonyl phenyl ether 8.40 4.28 −4.12 10.30 1.90 9.97 1.57
POE(5) nonyl phenyl ether 10.30 4.61 −5.69 10.95 0.65 10.91 0.61
POE(6) nonyl phenyl ether 11.40 4.94 −6.46 11.52 0.12 11.66 0.26
POE(8) nonyl phenyl ether 13.00 5.60 −7.40 12.48 −0.52 12.84 −0.16
POE(9) nonyl phenyl ether 13.00 5.93 −7.07 12.89 −0.11 13.31 0.31
POE(10) nonyl phenyl ether 13.40 6.26 −7.14 13.27 −0.13 13.72 0.32
POE(11) nonyl phenyl ether 13.80 6.59 −7.21 13.62 −0.18 14.09 0.29
POE(12) nonyl phenyl ether 14.10 6.92 −7.18 13.95 −0.15 14.42 0.32
POE(13) nonyl phenyl ether 14.40 7.25 −7.15 14.25 −0.15 14.73 0.33
POE(14) nonyl phenyl ether 14.70 7.58 −7.12 14.53 −0.17 15.00 0.30
POE(15) nonyl phenyl ether 15.00 7.91 −7.09 14.79 −0.21 15.26 0.26
POE(20) nonyl phenyl ether 16.00 9.56 −6.44 15.91 −0.09 16.27 0.27
POE(30) nonyl phenyl ether 17.10 12.86 −4.24 17.43 0.33 17.54 0.44
POE(40) nonyl phenyl ether 17.70 16.16 −1.54 18.42 0.72 18.29 0.59
POE(50) nonyl phenyl ether 18.20 19.46 1.26 19.09 0.89 18.75 0.55
POE(100) nonyl phenyl ether 19.00 35.96 16.96 20.44 1.44 19.72 0.72
POE(150) dinonyl phenyl ether 19.00 48.19 29.19 16.69 −2.31 16.58 −2.42

Polyhydric alcohol ester

Hexyl laurate 10.5 1.33 −9.18 3.85 −6.65 3.85 −6.65
Glycol stearate 2.4 2.28 −0.13 2.09 −0.31 2.09 −0.31
Glycol distearate 2.1 −5.30 −7.40 −2.54 −4.64 −2.54 −4.64
Propylene glycol laurate 4.5 4.65 0.15 4.74 0.24 4.74 0.24
Propylene glycol myristate 3.9 3.70 −0.20 3.82 −0.08 3.82 −0.08
Propylene glycol stearate 3.4 1.80 −1.60 1.99 −1.41 1.99 −1.41
Propylene glycol oleate 2.3 1.80 −0.50 1.99 −0.31 1.99 −0.31
Glycerol stearate 3.8 3.70 −0.10 2.81 −0.99 2.81 −0.99
Glycerol-12-hydroxyl stearate 1.9 5.60 3.70 5.07 3.17 5.07 3.17
Glycerol oleate 3.4 3.70 0.30 2.81 −0.59 2.81 −0.59
Glycerol laurate 5.3 6.55 1.25 5.56 0.26 5.56 0.26
Glycerol myristate 5.0 5.60 0.60 4.64 −0.36 4.64 −0.36
Glycerol lactate 3.5 12.73 9.23 11.00 7.50 11.00 7.50
Pentaerythritol stearate 2.3 7.03 4.73 2.95 0.65 2.95 0.65

Amine
POE(4) dodecyl amine 9.75 13.26 3.51 10.38 0.63 9.56 −0.19
POE(5) dodecyl amine 10.86 13.59 2.73 11.15 0.29 11.31 0.45
POE(6) dodecyl amine 11.76 13.92 2.16 11.80 0.04 12.53 0.77
POE(7) dodecyl amine 12.49 14.25 1.76 12.37 0.12 13.47 0.98
POE(8) dodecyl amine 13.11 14.58 1.47 12.87 0.24 14.23 1.12
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 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450 449

Table 3 (continued)
Surfactant HLBa Davies method ECL method
HLBc  Eq. (5) Eq. (5 )
HLBc  HLBc 
POE(9) dodecyl amine 13.63 14.91 1.28 13.33 0.30 14.86 1.23
POE(2) octadecyl amine 8.50 9.75 1.25 5.36 3.14 3.43 −5.07
POE(50) octadecyl amine 17.80 25.59 7.79 17.13 0.67 18.49 0.69
a HLB data are obtained from Ref. [23]. Since the HLB value of the same surfactant may differ a little from one manufacturer to another, the average value of all
manufacturers is adopted.

Table 4
The HLB values of Pluronic L, F, P, R block copolymers calculated both by the ECL method and the Davies method
Copolymer Mol wt Average no. of Average no. of HLBa Davies method ECL method
EO groups PO groups HLBc  Eq. (5) Eq. (5 )
HLBc  HLBc 
L31 1100 2.5 17.0 5.0 7.79 3.29 7.43 2.43 5.24 0.24
L35 1900 21.3 16.4 19.0 14.09 −4.41 22.73 3.73 23.64 4.64
F38 4700 84.3 17.1 31.0 34.77 4.27 32.97 1.97 32.64 1.64
L42 1630 7.4 22.5 8.0 8.59 0.59 13.54 5.54 12.16 4.16
L43 1850 12.6 22.3 12.0 10.33 −1.67 17.05 5.05 17.28 5.28
L44 2200 20.0 22.7 16.0 12.70 −3.30 20.29 4.29 21.15 5.15
L61 2000 4.5 31.0 3.0 6.37 3.37 2.85 −0.15 2.38 −0.62
L62 2500 11.4 34.4 7.0 8.10 1.10 12.63 5.63 12.59 5.59
L63 2650 18.0 31.9 11.0 10.68 −0.32 16.67 5.67 17.46 6.46
L64 2900 26.4 30.0 15.0 13.72 −1.28 20.20 5.20 21.15 6.15
P65 3400 38.6 29.3 17.0 17.86 0.86 23.44 6.44 24.23 7.23
F68 8400 152.5 28.9 29.0 55.52 26.52 32.30 3.30 30.78 1.78
L72 2750 12.5 37.9 7.0 7.96 0.96 12.20 5.20 12.39 5.39
P75 4150 47.1 35.7 17.0 19.70 2.70 23.02 6.02 23.6 6.6
F77 6600 104.9 34.1 25.0 39.01 14.01 29.01 4.01 28.32 3.32
L81 2750 6.3 42.7 2.0 5.18 3.18 6.35 4.35 4.17 2.17
P84 4200 38.1 43.4 14.0 15.60 1.60 18.98 4.98 19.79 5.79
P85 4600 52.3 39.7 16.0 20.82 4.82 22.62 6.62 23.06 7.06
F87 7700 122.4 39.8 24.0 43.93 19.93 28.04 4.04 26.88 2.88
F88 11,400 207.3 39.3 28.0 72.02 44.02 29.96 1.96 28.57 0.57
L92 3650 16.6 50.3 6.0 7.45 1.95 10.40 4.40 11.07 5.07
F98 13,000 236.1 44.8 28.0 80.71 52.71 28.51 0.51 27.41 −0.59
L101 3800 8.6 59.0 1.0 3.53 2.53 3.21 2.21 2.43 1.43
P103 4950 33.8 59.7 9.0 11.70 2.70 12.99 3.99 13.86 4.86
P104 5900 53.6 61.0 13.0 18.06 5.06 16.24 3.24 16.64 3.64
P105 6500 73.9 56.0 15.0 25.49 10.49 20.09 5.09 19.99 4.99
F108 14,600 265.5 50.3 27.0 89.57 62.57 26.95 −0.05 26.22 −0.78
L121 4400 10.0 68.3 1.0 2.58 1.58 1.34 0.34 0.96 −0.04
L122 5000 22.7 68.9 4.0 6.68 2.68 7.03 3.03 7.97 3.97
P123 5750 39.2 69.3 8.0 12.05 4.05 11.21 3.21 11.98 3.98
F127 12,600 200.4 65.2 22.0 65.87 43.87 21.90 −0.10 20.38 −1.62
10R5 1950 23.1 17.2 15.0 14.92 −0.10 14.94 −0.06 15.26 0.26
10R8 4550 92.4 17.2 19.0 37.80 18.80 19.18 0.18 18.35 −0.65
12R3 1800 11.8 20.7 7.0 10.69 3.70 11.17 4.17 11.64 4.64
17R1 1900 4.3 29.3 3.0 6.92 3.90 5.25 2.25 5.04 2.04
17R2 2150 9.7 29.3 6.0 8.71 2.70 7.87 1.87 8.32 2.32
17R4 2650 26.0 29.3 12.0 14.07 2.10 12.00 0.00 12.26 0.26
17R8 7000 156.0 29.3 16.0 56.97 41.0 17.04 1.04 15.75 −0.25
22R4 3350 33.6 37.9 10.0 15.27 5.30 10.63 0.63 10.73 0.73
25R1 2700 6.4 43.0 2.0 5.52 3.50 2.51 0.51 2.68 0.68
25R2 3100 14.3 43.0 4.0 8.14 4.10 5.21 1.21 5.68 1.68
25R4 3600 38.1 43.0 8.0 16.00 8.00 10.10 2.10 10.14 2.14
25R5 4250 57.2 43.0 10.0 22.29 12.30 11.53 1.53 11.23 1.23
25R8 8550 228.6 43.0 13.0 78.87 65.90 15.49 2.49 14.10 1.10
31R1 3250 7.9 53.4 1.0 4.47 3.50 0.49 −0.51 0.80 −0.20
31R2 3300 17.7 53.4 2.0 7.71 5.70 4.60 2.60 5.06 3.06
31R4 4150 47.2 53.4 7.0 17.45 10.40 8.83 1.83 8.75 1.75
a The HLB values are obtained from the data reported by BASF Corp.
450 X. Guo et al. / Journal of Colloid and Interface Science 298 (2006) 441–450

Table 5
HLB values of Span and Tween surfactants calculated both by the ECL method and the Davies method
Trademark Surfactant HLBa Davies method ECL method
HLBc  Eq. (5) Eq. (5 )
HLBc  HLBc 
Span-85 Sorbitan trioleate 1.8 2.13 0.33 1.65 −0.15 1.65 −0.15
Span-65 Sorbitan tristearate 2.1 2.13 0.02 1.65 −0.45 1.65 −0.45
Span-80 Sorbitan monoolieate 4.3 5.68 1.38 5.23 0.93 5.23 0.93
Span-60 Sorbitan monostearate 4.7 5.68 0.98 5.23 0.53 5.23 0.53
Span-40 Sorbitan monopalmitate 6.7 6.63 −0.08 6.15 −0.55 6.15 −0.55
Span-20 Sorbitan monolaurate 8.6 8.53 −0.07 7.98 −0.62 7.98 −0.62
Tween-65 POE(20) sorbitan tristearate 10.5 11.20 0.70 11.05 0.55 11.41 0.91
Tween-85 POE(20) sorbitan trioleate 11.0 11.20 0.20 11.05 0.05 11.41 0.41
Tween-61 POE(4) sorbitan monostearate 9.6 10.13 0.53 9.03 −0.57 8.70 −0.90
Tween-81 POE(4) sorbitan monoolieate 10.0 10.13 0.13 9.03 −0.97 8.70 −1.30
Tween-21 POE(4) sorbitan monolaurate 13.3 14.05 0.74 11.78 −1.52 11.45 −1.85
Tween-60 POE(20) sorbitan monostearate 14.9 16.48 1.58 14.63 −0.27 15.00 0.10
Tween-80 POE(20) sorbitan monoolieate 15.0 16.48 1.48 14.63 −0.37 15.00 0.00
Tween-40 POE(40) sorbitan monopalmitate 15.6 17.43 1.83 15.55 −0.05 15.91 0.31
Tween-20 POE(20) sorbitan monolaurate 16.7 19.33 2.63 17.38 0.68 17.75 1.05
a The HLB values are obtained from the data reported by ICI Americas Inc.

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