Colloids and Surfaces A: Physicochem. Eng.

Aspects 252 (2005) 79–85

Effect of EO and PO positions in nonionic surfactants on surfactant

properties and demulsification performance
Jiangying Wu, Yuming Xu∗ , Tadeusz Dabros, Hassan Hamza
CANMET Energy Technology Centre – Devon, Natural Resources Canada, 1 Oil Patch Drive, Devon, Alta., Canada T9G 1A8

Received 5 May 2004; accepted 27 September 2004

Abstract

Demulsifiers provide an important means of breaking water-in-oil emulsions that occur in industrial processes. The properties and the
performance of 20 blocked copolymers from four surfactant families were investigated and three pairs isomeric compounds were com-
pared. The results show that different positions of the ethylene oxide (EO) and propylene oxide (PO) in block copolymers lead to different
hydrophile–lipophile balances (HLB) of surfactant. The sequential block copolymer is more hydrophilic than the reverse-sequential one with
similar chemical composition. The greater the molecular weight, the greater the difference between the hydrophile–lipophile balances of the
two surfactant types. Generally, the demulsification performance of sequential copolymers is better than that of reverse-sequential copolymers.
Position isomerism of the surfactant affects demulsification performance by changing the hydrophile–lipophile balance, interfacial properties,
and steric characteristics at the interface.
Crown Copyright © 2004 Published by Elsevier B.V. All rights reserved.

Keywords: Water-in-oil emulsion; Nonionic surfactant; Position isomerism; Emulsion breaker; Demulsification

1. Introduction sion breaking process, demulsification performance was also

Chemical demulsification is an important method of treat-
ing water-in-oil emulsion, in which chemicals (surfactants)
are added to the emulsions. Thousands of surfactants can be
synthesized by changing the acceptor, ratio, amount, and se-
quence of hydrophobic and hydrophilic groups. A literature
survey turns up between 2000 and 3000 patents referring di-
rectly to this subject [1]. Therefore, the design, selection, and
formulation of an efficient emulsion breaker are obviously a
complex challenge.
To address this challenge, the role of surfactant structure
in destabilizing water-in-oil emulsions should be well un-
derstood. The mechanism of demulsification and the prin-
cipal role of the surfactant in destabilization of emulsion
have been studied by many researchers [2–8]. Together with
the research work on the physics-based model of the emul-
∗ Corresponding author.
E-mail address: yxu@nrcan.gc.ca (Y. Xu).
studied in terms of the physical and chemical properties of
demulsifiers. Krawczyk et al. believed that partitioning of the
demulsifier is important factor in the mechanism of demulsi-
fication. They claimed that demulsifiers with partition coeffi-
cients close to unity exhibit superior performance [7]. Cooper
et al. and Averyard et al. noted that the hydrophile–lipophile
balance (HLB) is an important parameter for effective demul-
sification [9,10]. Shetty et al. concluded that a demulsifier
containing a high percentage of hydrophilic groups and hav-
ing a low molecular weight can perform very well [11]. Wu
et al. concluded from experimental results that the perfor-
mance of demulsifiers is correlated to both their molecular
weights and relative solubility numbers (RSN) which has
been defined empirically as the volume, in milliliters, of dis-
tilled water needed to produce persistent turbidity in a sol-
vent system consisting of 1 g surfactant sample and 30 mL
benzene/dioxane solvent. An optimal RSN value for demul-
sification exists for surfactants belonging to the same family
[12]. Marquez-Silva et al. proposed an empirical model that

0927-7757/$ – see front matter. Crown Copyright © 2004 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.09.034
80 J. Wu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 79–85

established a relation between the nature of the crude oil, the Table 1
associated water salinity, and the demulsifier hydrophilicity Surfactants used in this study
[13]; Berger et al., however, found no correlation between Code Formula Mn EO%
RSN, HLB, and demulsifier performance [14]. Abdel-Azim Pluronic
et al. discussed the influences of the number of aromatic L61 HEO2 PO31 EO2 2000 10
rings in the surfactant molecules and the degree of substi- L81 HEO3 PO43 EO3 2800 10
L43 HEO6 PO22 EO6 1850 30
tution in the aromatic rings. These authors found that for P103 HEO15 PO53 EO15 4400 30
monocyclic aromatic PPPEA, the di-substituted propylene P123 HEO20 PO70 EO20 5800 30
oxide (PO)–ethylene oxide (EO) aromatic amines exhibit L44 HEO10 PO23 EO10 2200 40
demulsification efficiency superior to that of their mono- L64 HEO13 PO30 EO13 2900 40
substituted counterparts. Bicyclic PO–EO aromatic amine P84 HEO19 PO43 EO19 4200 40
L35 HEO11 PO16 EO11 1900 50
performs more efficiently than its monocyclic counterparts F38 HEO43 PO16 EO43 4700 80
[15]. In summary, previous researchers have related some of F68 HEO76 PO29 EO76 8400 80
the characteristics of emulsion breakers to demulsification
PluronicR
performance. In this paper, we investigated the effects of EO 31R1 HPO26 EO7 PO26 3300 10
and PO position (position isomerism) in blocked copolymer 17R4 HPO14 EO24 PO14 2700 40
surfactants on their properties and performance as emulsion 25R4 HPO19 EO33 PO19 3600 40
breakers. 10R5 HPO8 EO22 PO8 2000 50
Tetronic
701 [ CH2 N[(PO)14 (EO)2 H]2]2 3600 10
904 [ CH2 N[(PO)17 (EO)15 H]2]2 6700 40
2. Experimental 1107 [ CH2 N[(PO)19 (EO)59 H]2]2 15000 70
TetronicR
2.1. Materials
150R1 [ CH2 N[(EO)5 (PO)31 H]2]2 8000 10
90R4 [ CH2 N[(EO)16 (PO)18 H]2]2 7200 40
Blocked ethylene oxide and propylene oxide copolymers
were supplied by BASF and were used as received. Their
commercial names are Pluronic, PluronicR, Tetronic, and
TetronicR. All of these surfactants are made of blocked PO bi-functional block copolymers. The composition and some
and EO. The simplified structures of these surfactants are of the properties of all the surfactants used in this paper are
shown in Fig. 1. The acceptor of Pluronic and PluronicR is listed in Table 1. As the table shows, the sequential surfac-
propylene glycol. The acceptor of Tetronic and TetronicR is tants have an EO block at each end of the molecule and a PO
ethylenediamine. Pluronic and Tetronic are sequential surfac- block in the centre, while the reverse sequential surfactants
tants, while PluronicR and TetronicR are reverse-sequential have a PO block at each end of the molecule and an EO block
surfactants. The term sequential means the acceptor reacts in the centre.
with PO first and then with EO. Reverse-sequential means Ethylene glycol dimethyl ether (analytical grade) and
the acceptor reacts with EO first and then with PO. Tetronic toluene (analytical grade) used for the RSN determinations
and TetronicR are tetra-functional block copolymers (one were purchased from Aldrich Chemicals and used as re-
molecule has four arms), while Pluronic and PluronicR are ceived. The bitumen sample was obtained from Syncrude
Canada Ltd. Toluene used for bitumen dilution was indus-
trial grade.

2.2. RSN determination

In this work, the RSN values of the surfactants were

determined by a recently developed titration method, in
which RSN solvent consists of toluene/ethylene glycol
dimethyl ether [16]. This parameter is used to represent the
hydrophile–lipophile balance; higher values mean greater hy-
drophilicity. Previous studies showed a linear correlation be-
tween RSN and HLB [16].

2.3. Interfacial tension measurement

Fig. 1. Simplified structures of molecules of Pluronic, PluronicR, Tetronic,

Interfacial tension and surface tension were determined by
and TetronicR. the Du Nouy Ring method using a Kruss K-12 tensiometer.
 J. Wu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 79–85 81

2.4. Preparation of stable water-in-oil emulsion

Bitumen was first diluted to a 5% solution with toluene.

The solution was then centrifuged at 4000 × g for 30 min at
25 ◦ C to remove the small quantity of residual fine solids.
The water-in-oil emulsion was prepared by mixing equal
weights of 5% bitumen-in-toluene solution and 0.01M
NaCl solution using a Polytron homogenizer at 20,000 rpm
for 3 min. The emulsion thus prepared was a very stable
water-in-oil emulsion that could remain stable without phase
separation for weeks.

2.5. Demulsification tests

The demulsification tests were conducted at 60 ◦ C using
gravitational settling. About 12 g of fresh emulsion was pre-
pared and transferred into a 15-mL graduated cone-shaped
centrifuge tube and aged for 10 min at 60 ◦ C. A pre-selected
amount of surfactant was injected into the emulsion using a
micropipette. After the contents in the tube had been shaken
in an oscillating shaker for 1 min, the tube was placed in a wa-
ter bath at 60 ◦ C to allow the emulsion to separate. The phase
separation was recorded as a function of time. During the
settling, the interface between the emulsion phase and water
phase was not easily observable, but the interface between
the top oil phase and emulsion was clearly visible. The oil
phase looked black and its water content was less than 1–2%.
Therefore, the movement of the oil/emulsion interface was
monitored with time. After settling for 1 h, about 1 mL of
sample was taken from 3 cm below the surface and its water
content was determined by Karl Fischer titration.
The performance of a surfactant was evaluated on the basis
of two criteria. The first was the rate at which the oil phase
was released as described by the percentage of oil resolution
from the emulsion calculated from:
100 Voil
Oil resolution (v%) = (1)
V ◦ oil
where Voil is the volume of separated oil phase and V ◦ oil is the
volume of oil in the initial emulsion, a known quantity. The
second criterion was the water concentration in the sample
taken 3 cm below the surface after settling for 1 h.
Fig. 2. Cloud points of Pluronic and PluronicR with different percentages
of EO and molecular weights (supplied by BASF).
The cloud point is the temperature below which a sin-
gle phase of molecular or micellar solution exists; above the
cloud point the surfactant loses sufficient water solubility
and a cloudy dispersion results [19]. Above this tempera-
ture, the surfactant also ceases to perform some or all of
its normal functions. So cloud point can be used to limit
the choice of nonionic surfactants for application in certain
processes. A suggestion was made to regard the cloud point
in solution of nonionic surfactant as a pseudophase inver-
sion. For polyoxyethylene-type surfactant, the cloud point
and the phase inversion temperature (PIT) are directly cor-
related when surfactant alone is dispersed in water. PIT is
defined as the temperature at which the hydrophile–lipophile
property of surfactant just balances at the interface [20]. So
for the polyoxyethylene-type surfactants, cloud point is re-
lated to the hydrophile–lipophile balance.
The changes of cloud points of Pluronic, PluronicR,
Tetronic, and TetronicR with percent EO and molecular
weight are shown in Figs. 2 and 3. All the data were supplied
by BASF [21]. Clearly, cloud point increases with increasing
percent EO. For the sequential surfactants, the cloud point

3. Results and discussion

3.1. Effect of position isomerism on

hydrophile–lipophile balance

HLB is an important parameter characterizing a surfactant

that can indicate its appropriate applications. Classical equa-
tions derived by Griffin and Davies were used to calculate the
HLB number of surfactants [17,18], however, these equations
consider only the chemical compositions, and the effect of po-
sition isomerism is not taken into account. Because HLB is
difficult to determine experimentally, we instead used cloud Fig. 3. Cloud points of Tetronic and TetronicR with different percentages
point and RSN to represent the hydrophile–lipophile balance. of EO and molecular weights (supplied by BASF).
82 J. Wu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 79–85
of those with less than 20% EO decreases with increasing
molecular weight, but for those with more than 40% EO,
the cloud point increases with increasing molecular weight.
For the reverse sequential-surfactants, the cloud point always
decreases with increasing molecular weight. The effect of po-
sition isomerism on the cloud point can also be observed from
Figs. 2 and 3. For the surfactants with low percent EO (such as
10% EO), there is not a large difference; but for the surfactants
with high percent EO, the cloud points differ significantly be-
tween the sequential and reverse-sequential surfactants hav-
ing the same percent EO and molecular weight. The cloud
point of a sequential surfactant is always higher than that of
a reverse-sequential one and the difference increases with in-
creasing molecular weight. RSN is another parameter directly
related to the hydrophile–lipophile balance of a nonionic sur-
factant. Linear correlations between RSN and HLB for differ-
ent surfactant families were established by Wu et al. [16]. The
higher the RSN value the greater the hydrophilicity of the sur-
factant. Several pairs of surfactants with the same composi-
tion but with different sequential arrays were chosen for RSN
determination. The data, listed in Table 2, show that a sequen-
tial block copolymer has a higher RSN value than the corre-
sponding reverse-sequential one that has similar PO and EO
numbers. As a result, when the chemical compositions are the
same, the sequential surfactant is more hydrophilic than the
reverse-sequential surfactant. The difference between RSN
values for sequential and reverse-sequential surfactants is
not significant for smaller-molecule surfactants (molecular
weight < 3000), however, this difference increases with in-
creasing molecular size and becomes very significant for
large molecules (molecular weight > 6000). The change in the
RSN difference between sequential and reverse-sequential
surfactants with molecular weight is also consistent with that
in the cloud point difference, as discussed in the previous
paragraph.
It is believed that the solubility of a nonionic surfactant in
water is related to the hydration of the oxyethylene groups.
The hydration of the ether oxygens by hydrogen bonding
should result in the binding of at least two water molecules
per EO group. In general, hydration numbers of 2–4 are often
found [20,22]. The amount of hydration water should there-
fore increase with increasing poly-EO chain length. How-
ever, for very long EO chains increased crowding may result
in dehydration, as evidenced by the reported results that the
Table 2
RSN values of selected surfactants
Code Formula Mn EO%
L81 HEO3 PO43 EO3 2800 10
31R1 HPO26 EO7 PO26 3300 10
L64 HEO13 PO30 EO13 2900 40
17R4 HPO14 EO24 PO14 2700 40
L35 HEO11 PO16 EO11 1900 50
10R5 HPO8 EO22 PO8 2000 50
904 [ CH2 N[(PO)17 (EO)15 H]2]2 6700 40
90R4 [ CH2 N[(EO)16 (PO)18 H]2]2 7200 40
water/EO mole ratio is 6 for C12 EO12 [23] but only 2.35
for C12 EO28 [24]. For Pluronic and PluronicR, the length
of each poly-EO chain in the sequential molecules is only
half of that in the reverse-sequential molecules. Therefore,
for molecules with the same EO number, the EO in sequen-
tial surfactant hydrates with more water molecules, leading
to higher hydrophilicity. For TetronicR, all the EO groups are
located in the centre of the molecule; the EO blocks from the
four arms are very close to each other and the crowded EO
moiety results in much less hydration than for Tetronic, in
which the EO blocks are at the end of each arm. For smaller
molecules, this steric effect on hydration can be neglected.
The above results show that position isomerism strongly
affects the hydrophile–lipophile balance. The sequential
block copolymer is more hydrophilic than reverse-sequential
surfactants with the same chemical composition. It should
be pointed out that estimation of HLB based on chemical
composition using classic equations such as those proposed
by Griffin or Davies [17,18] is unable to differentiate be-
tween sequential and reverse-sequential isomers. Therefore,
the results from the present work suggest that the effect of
position isomerism should be taken into account when esti-
mating HLB, cloud point, and other properties by the group
contribution method.
3.2. Effect of position isomerism on demulsification
performance
The demulsification performance of 20 surfactants from
four families including Pluronic, PluronicR, Tetronic, and
TetronicR were evaluated using the model water-in-oil emul-
sion. The chemical composition of the surfactants can be
found in Table 1. The oil resolution rates of the water-in-
oil emulsion with addition of these surfactants are shown in
Figs. 4–6. The dosage of the surfactant is 200 ppm based
on the weight of oil phase. The water concentrations in the
separated oil phase (or emulsion) samples taken 3 cm below
RSN
11.4
9.95
18.1
17.1
22.3
21.0
28.0
Fig. 4. Oil-phase resolution for water-in-oil emulsion with addition of
16.9
Pluronic surfactants.
 J. Wu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 79–85 83

Table 3
Water concentrations in oil phase (or emulsion) from 3 cm below the surface
Code EO% Water concentration (wt.%)
Pluronic
L61 10 49.01
L81 10 38.95
L43 30 36.52
P123 30 0.10
L44 40 0.27
L64 40 0.15
P84 40 0.08
L35 50 0.73
F38 80 1.55
F68 80 0.24
PluronicR
37R1 10 47.36
17R4 40 42.17
25R4 40 10.31
10R5 50 39.34

Fig. 5. Oil-phase resolution for water-in-oil emulsion with addition of
PluronicR surfactants.
the top surface after 1 h gravitational settling are listed in
Table 3.
Fig. 4 shows that, for the Pluronic family, the oil-phase
separation rate increases with increasing EO percentage in
surfactant molecules. For this type of water-in-oil emulsion,
the Pluronic surfactants containing less than 30% EO do not
break the emulsion efficiently, while those containing more
than 40% EO can effectively break the emulsion. In fact, the
Pluronic surfactant containing 80% EO seems to function as
a very good demulsifier; the emulsion can be broken entirely
in 1 min. Fig. 5 shows the oil resolution as a function of time
for the PluronicR surfactant family. As can be seen, the oil
resolution for all surfactants is very slow for EO percentage in
the studied range of 10–50%. For example, the oil resolution
is less than 20% after 1 h settling when PluronicR surfac-
tants containing 40% EO are applied, as compared to about
Fig. 6. Oil-phase resolution for water-in-oil emulsion with addition of
Tetronic and TetronicR surfactants.
Tetronic and TetronicR
701 10 34.49
904 40 0.06
1107 70 0.05
150R1 10 8.49
90R4 40 6.14
90% when Pluronic surfactants containing similar EO per-
centages are used. The oil resolution results for the Tetronic
and TetronicR surfactants are shown in Fig. 6. Similar to
Pluronic and PluronicR, Tetronic surfactants containing 40
or 70% EO achieve rapid oil resolution, dry oil, and clear
water phase. However, the oil resolution for TetronicR con-
taining 40% EO is still less than 10% after 1 h settling.
From the data in Table 3, the water concentrations in the
samples from 3 cm below the surface fall into three ranges,
more than 30%, 5–10%, and less than 2%. Combining these
water concentrations with oil resolution rates, we can clas-
sify the surfactants into three groups by performance: the
emulsion is broken, partly broken, or not broken at all. If
the emulsion is broken, the oil phase is black, the water con-
centration is less than 2%, and the separated water phase
is clear. If the emulsion is partly broken, there is a lit-
tle black oil phase and the emulsion is separated into two
phases, an oil-rich phase and a water-rich phase. The oil-
rich phase is dark brown and the water-rich phase is light
brown. The oil-rich phase has a water concentration around
10% and only a small amount appears as free water. If the
emulsion is not broken, all of the emulsion remains yellow
during settling, and the water concentration is more than
30%.
Based on the above definition of the three levels of
emulsion-breaking performance, the four series of surfac-
tants used in this work can be described as follows: Pluronic
surfactants containing more than 30% EO can break the emul-
sion; surfactants containing less than 10% EO cannot break
the emulsion. For the PluronicR series, almost all surfactants
studied in this work are unable to break the prepared water-
in-oil emulsion. Tetronic surfactants containing over 40% EO
84 J. Wu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 79–85

can break the emulsion very effectively, whereas TetronicR Table 4

can only partly break this kind of emulsion. Interfacial tension and surface tension of 904, 90R4, L64, and 17R4
In summary, the sequential block copolymer containing IFT (mN/m) SFT (mN/m)
more than 40% EO can break this type of emulsion, and 200 ppm in 200 ppm in 5% diluted
the rate of emulsion breakage increases with increasing EO toluene/DI water bitumen/0.01M NaCl
percentage. The reverse sequential copolymer, regardless the 904 0.41 <0.3 39.04
percentage of EO, cannot break or can only partly break the 90R4 6.05 5.15 42.86
emulsion. L64 5.19 7.14 43.15
The difference in the demulsification performance be- 17R4 12.36 12.04 45.41
tween the sequential and reverse sequential surfactants is due
to the positioning effect of EO blocks, which may change the
than that of 90R4, but the interfacial tension of the 90R4
surfactant hydrophile–lipophile balance (RSN) and surface
is significantly higher than that of 904. (c) In addition to the
and interfacial properties and, more importantly, cause dif-
above two factors, the steric effect may also play an important
ferent steric effects. When the block copolymer surfactant
role, as discussed earlier. Therefore, in this first case, posi-
is adsorbed at the water/oil interface, the hydrophobic block
tion isomerism affects demulsifier performance by changing
adsorbs in the oil phase while the hydrophilic block tends to
its hydrophile–lipophile balance, interfacial tension, and the
stay in the water phase. We can speculate that, for the sequen-
degree of the steric effect.
tial surfactant, the two short EO blocks at the both ends of the
The second pair, L64 and 17R4, have low molecular
molecule attach to water droplets while the hydrophobic moi-
weights (2700 and 2900, respectively) and the same EO
ety (PO block, in the centre of the molecule) orients toward
percentages (40%). The corresponding oil phase separation
the bulk oil phase and produces an interface with negligible
rate is shown in Fig. 7 and the water concentration can be
steric repulsion. On the other hand, for the reverse-sequential
found in Table 3. The results indicate that L64 can break
block copolymer, the hydrophobic tail is branched into the
the emulsion but 17R4 cannot. As discussed earlier, because
oil phase and extends the shear plane and inhibits aggrega-
of the low molecular weights and short EO chains, their
tion by maintaining droplet separation. Most significantly,
hydrophile–lipophile balance differed only marginally (RSN
droplet coalescence is slowed down. This may explain why
values differed by about 1). This means that the two surfac-
reverse-sequential surfactants cannot or can only partly break
tants will result in similar partitioning between the oil and
the emulsion. Reverse-sequential surfactants with highly hy-
water phases.
drophilic properties can cause some large droplets to aggre-
We then further investigated the surface and interfacial
gate and settle, but coalescence is difficult because of steric
properties of L64 and 17R4 by determining the surface ten-
effects.
sions and interfacial tensions. The data listed in Table 4 show
In order to examine the effect of position isomerism on
that the surface tensions of L64 and 17R4 are slightly differ-
demulsification performance in more detail, three pairs of
ent, but the interfacial tension of L64 is much smaller than
surfactants, 904 and 90R4, L64 and 17R4, and L35 and 10R5,
that of 17R4. The steric effect should also play a role between
were chosen to represent for three different scenarios. Each
the two surfactants. Therefore, in this second case, position
pair had very similar chemical compositions but one surfac-
isomerism affects demulsification performance by affecting
tant in each pair was sequential while another was reverse-
the interfacial properties and changing the steric effect.
sequential. Their properties can be found in Table 2.
The first pair, 904 and 90R4, have molecular weights
around 7000; both surfactants contain 40% EO. Although
the block PO and EO chain lengths in these two surfactants
are almost the same, their demulsification efficiencies showed
significant differences. The demulsification performance of
904 is much better than that of 90R4, as shown in Fig. 6.
For 904, very dry oil phase was obtained in 5 min and 87%
water separated out in 1 h of gravitational settling; but 90R4
can only break the emulsion very marginally. This perfor-
mance difference may be due to the following factors: (a)
Because of the high molecular weight and long EO chains,
position isomerism does affect the hydrophile–lipophile bal-
ance significantly. The RSN of 904 is 28 while the RSN of
90R4 is only 16.9. (b) Position isomerism may also affect
the interfacial properties such as interfacial tension. We mea-
sured the surface tension and interfacial tension of this pair
of surfactants and the results are reported in Table 4. As the Fig. 7. Comparison of oil resolution in water-in-oil emulsion with addition
data indicate, the surface tension of the 904 is slightly lower of Pluronic and PluronicR surfactants.
 J. Wu et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 252 (2005) 79–85
Fig. 8. Interfacial tension at different concentrations of L35 and 10R5.
The third pair, L35 and 10R5, also have very low
molecular weights and, as a result, similar RSN values or
hydrophile–lipophile balance. The interfacial tensions for
both of the surfactants at different concentrations, as shown
in Fig. 8, are almost the same. The corresponding oil resolu-
tion rate is also shown in Fig. 7 and the water concentrations
in the top oil phase are listed in Table 3. The results show
that L35 can break the emulsion but 10R5 cannot. Because
both surfactants have almost the same hydrophile–lipophile
balance and interfacial tensions, the difference in the
demulsification performance may only be related to steric
effects.
4. Conclusions
Position isomerism may strongly affect the hydrophile–
lipophile balance of a surfactant. In general, when the chem-
ical compositions are the same, sequential block copolymers
are more hydrophilic than reverse-sequential surfactants, es-
pecially for large molecules. These effects should be consid-
ered when calculating the HLB number and cloud point of a
surfactant by the group contribution method.
Generally, a sequential block copolymer with more than
40% EO can break the water-in-oil emulsion prepared in this
work, and the emulsion breakage rate increases with increas-
ing EO percentage. However, reverse-sequential copolymer,
even if it contains a high percentage of EO, cannot or can
only partly break the emulsion.
85
Position isomerism in surfactants affects demulsification
performance by changing the hydrophile–lipophile balance,
interfacial properties, and steric characteristics at the inter-
face.
Acknowledgement
We thank Shawna Hnatiuk of BASF for providing surfac-
tant samples and some cloud point data.
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